Polymerization catalyst compositions containing metallocene complexes and polymers produced by using the same

ABSTRACT

The present invention provides a novel catalyst composition comprising a metallocene complex, and a novel producing method for various polymer compounds. Preferably, the invention provides a novel polymer compound, and a producing method thereof. Specifically, the invention provides a polymerization catalyst composition, comprising:
         (1) a metallocene complex represented by the general formula (I), including:
           a central metal M which is a group III metal atom or a lanthanoid metal atom;   a ligand Cp* bound to the central metal and including a substituted or unsubstituted cyclopentadienyl derivative;   monoanionic ligands Q 1  and Q 2 ; and   w neutral Lewis base L; and   
           (2) an ionic compound composed of a non-ligand anion and a cation:       

                         
where w represents an integer of 0 to 3.

This application is a Divisional of U.S. application Ser. No.13/167,159, filed Jun. 23, 2011, now abandoned which is a Divisional ofU.S. application Ser. No. 11/631,381, filed Feb. 2, 2007, now U.S. Pat.No. 7,994,267, which is a national stage application of Internationalapplication No. PCT/JP2005/012254, filed Jul. 1, 2005.

TECHNICAL FIELD

The present invention relates to a polymerization catalyst compositioncontaining a metallocene complex, and more particularly to apolymerization catalyst composition, in which a central metal in themetallocene complex is a group III metal or a lanthanoid metal.

Further, the present invention relates to a production method of apolymer compound, which is characterized by using the polymerizationcatalyst.

Furthermore, the present invention relates to a polymer compound whichmay be produced by using the polymerization catalyst composition,particularly to a styrene high-syndiotactic polymer and astyrene-ethylene high-syndiotactic copolymer.

BACKGROUND ART

A metallocene complex is a compound being used as one of catalystcomponents in various polymerization reactions, and also is a complexcompound which has a central metal bound with one or morecyclopentadienyl or derivatives thereof. Of those, a metallocenecomplex, which has a central metal bound with one cyclopentadienyl orone derivative thereof, may be referred to as “half metallocene complex”or the like.

A metallocene complex has completely different characteristics(including a catalyst activity for a polymerization reaction) dependingon the type of its central metal. For example, the following reportshave been made for a metallocene complex which has a central metal of agroup III metal or a lanthanoid metal atom.

1. There is disclosed that a complex exemplified by the structuralformula (II) can be used as a component of a polymerization catalystsystem (see Patent Document 1). The complex disclosed in the document ischaracterized by including a crosslinking type ligand which hascyclopentadienyl (or a derivative thereof).

In the formula, M represents a group III metal or a lanthanoid metal, Arepresents a monoanionic crosslinking type ligand having acyclopentadienyl ring or the like, Q represents a monoanionic ligand, Lrepresents a neutral Lewis base, and w represents an integer of 0 to 3.

2. There is known a hydrido complex represented by (C₅Me₄SiMe₃)LnH₂(THF)(Ln represents a group III metal or a lanthanoid metal. Same holds truefor the following) (see, for example, Non-patent document 1). A complexrepresented by (C₅Me₄SiMe₃)Ln(CH₂SiMe₃)₂(THF), which is used as aprecursor for the hydrido complex, is also known.

In addition, it is reported that [(C₅Me₄SiMe₃)YH₂]₄(THF) (tetranuclearcomplex) of the (C₅Me₄SiMe₃)LnH₂(THF) is reacted with styrene to give a1:1 adduct and shows no polymerization activity (see, for example,Non-patent document 6).

3. It is known that, of the above-mentioned(C₅Me₄SiMe₃)Ln(CH₂SiMe₃)₂(THF), a complex having yttrium (Y) as Ln hasno polymerization activity for styrene (see Non-patent document 2).

4. Further, a complex represented by (C₅Me₄SiMe₃)La(CH₂(SiMe₃)₂)₂(THF)is known, and it is reported that the complex can serve as a catalystfor a polystyrene polymerization by being combined with methylaminoxane(MAO) or by itself to give an atactic polystyrene (see Non-patentdocument 3).

However, utility of a metallocene complex (particularly a metallocenecomplex having a central metal of a group III metal or a lanthanoidmetal) as a polymerization catalyst component has not been sufficientlyelucidated, so additional studies have been desired.

On the other hand, as a styrene polymer, a syndiotactic styrene polymer(sPS) which can be obtained by a polymerization reaction using ametallocene complex has been industrially produced, as well as anatactic styrene polymer which is referred to as a general gradepolystyrene (GPPS), a high-impact resistant polystyrene (HIPS), or thelike. Synthesis of sPS was announced by Idemitsu Kosan Co., Ltd. in1986, and performed by using a catalyst system which includes a titaniummetallocene complex (see, for example, Non-patent document 4). As thecatalyst system, CpTiX₃/MAO or CpTiR₃/B(C₆F₅)₃ (Cp represents asubstituted or unsubstituted cyclopentdienyl or indenyl, X represents ahalide or alkoxy, R represents an alkyl, and MAO representsmethylaminoxane) or the like is mainly used.

The thus-synthesized sPS is characterized by having a slightly broadmolecular weight distribution irrespective of high syndiotacticity (see,for example, Patent-Documents 2 and 3). Therefore, sPS with a narrowermolecular weight distribution has been a compound of interest.

sPS is a polymer which has a high melting point of about 270° C., andadvantages such as suitable crystallinity, excellent heat resistance,chemical resistance, and dimension stability, and thus is widely used inindustry. Meanwhile, however, it is pointed out that sPS is difficult tobe formed or the like.

On the other hand, some reports have been made for synthesis of anethylene-styrene copolymer (see Non-patent document 5). Each ofethylene-styrene copolymers in those reports is a copolymer having noregio selectivity or a copolymer having no stereoregularity regarding achain of styrene structural units. Thus, an ethylene-styrene copolymer,which has regio selectivity and high stereoregularity (particularlysyndiotacticity) with respect to styrene structural units, has been aninteresting compound.

Further, there is reported a method of synthesizing an isoprene-styrenecopolymer having styrene structural units with high syndiotacticityusing a catalyst of CpTiCl₃/MAO (Cp is cyclopentadienyl) (see Non-patentdocument 10). A catalyst activity in the polymerization reaction isinsufficient, so additional improvement has been required. Moreover,many physical properties of the isoprene-styrene copolymer to besynthesized have remained unclarified.

In a polymer of a cyclic olefin, a movement of a polymer main chain ofthe cyclic olefin is restricted compared to a polymer of a non-cyclicolefin, so the polymer of a cyclic olefins is expected to have excellentheat resistance, strength, and elasticity modulus. In addition, thecyclic olefin has an expanding potential to be used as an opticalmaterial. However, the cyclic olefin compound generally has lowpolymerization activity because its molecule is bulky, so the number ofan effective polymerization catalyst system is limited.

In contrast, there is reported a 1,3-cyclohexadiene polymer which isobtained by polymerizing 1,3-cyclohexadiene, that is one of cyclicolefins, by using a specific nickel catalyst (Non-patent document 7).The polymer is characterized by being a polymer obtained by1,4-selective addition polymerization of 1,3-cyclohexadiene. Further, itis suggested that the polymer is cis-syndiotactic. However, no specificreports regarding syndiotacticity, molecular weight, and the likethereof have been made.

Further, there are few reports on a 1,3-cyclohexadiene copolymer, so acopolymer of 1,3-cyclohexadiene and another olefin is an interestingcompound. As one of a few examples, there is reported a copolymer of1,3-cyclohexadiene and styrene, which is obtained by anioniccopolymerization using alkyl lithium. However, the copolymer has no siteregularity and stereoregularity.

On the other hand, as a polymer of norbornenes whichisoneofcyclicolefins, therehavebeenknownanopen-ringmetathesis polymer, acopolymer of norbornenes and ethylene, and the like. Particularly, thecopolymer of norbornenes and ethylene has excellent transparency andheat resistance, so the copolymer is expected to be developed as anoptical material (see Non-patent document 8). The inventors of thepresent invention have thought that a copolymer (terpolymer) includingnorbornenes, ethylene, and an aromatic component has physical properties(for example, UV blocking properties) equal to or superior to those of acopolymer of norbornenes and ethylene, and have made a study ofproduction of the terpolymer.

Further, dicyclopentadiene as one of norbornenes has a C═C double bondderived from a norbornene structure and a C═C bond derived fromcyclopentene. A copolymer of dicyclopentadiene and ethylene is also aninteresting compound like norbornene. Recently, there has been reportedthat the copolymer of dicyclopentadiene and ethylene can be synthesizedby using a specific Zr complex as a polymerization catalyst (Non-patentdocument 9). However, a copolymer of dicyclopentadiene and ethylenesynthesized according to the reported method, has a limited molecularweight and content of dicyclopentadiene.

Patent Document 1: WO 00/18808

Patent Document 2: JP 62-104818 A

Patent Document 3: JP 62-187708 A

Non-patent document 1: Z. Hou et al., Organometallics, 22, 1171 (2004)

Non-patent document 2: J. Okuda et al., Angew. Chem. Int. Ed., 38, 227(1999)

Non-patent document 3: K. Tanaka, M. Furo, E. Ihara, H. Yasuda, J.Polym. Sci. A: Polym. Chem. 39, 1382 (2001)

Non-patent document 4: N, Ishihara et al., Macromolecules, 19, 2464(1986)

Non-patent document 5: Mc Knight, A. L.; Chem. Rev. 98, 2587, (1998)

Non-patent document 6: Z. Hou et al., J. Am. Chem. Soc., 126, 1312(2004)

Non-patent document 7: S. Tanimura et al., Journal of Polymer Science:Part B: Polymer Physics, Vol. 39, 973-978 (2001)

Non-patent document 8: K. Nomura et al., Macromolecules, 36, 3797 (2003)

Non-patent document 9: Adriane G. Simanke et al., Journal of PolymerScience Part A: Polymer Chemistry, Vol. 40, 471-485 (2002)

Non-patent document 10: Pellecchia, C.; Proto, A.; Zambelli, A.,Macromolecules, 25, 4450 (1992)

DISCLOSURE OF THE INVENTION

1. An object of the present invention is to provide a novel catalystcomposition containing a metallocene complex. A further object of thepresent invention is to provide a production method of various kinds ofpolymer compounds using the catalyst composition. Preferably, a stillfurther object of the present invention is to provide a productionmethod of a novel polymer compound using the catalyst composition.

2. Meanwhile, the present invention provides a novel polymer compound.That is, an object of the present invention is to provide: (1) a styrenecopolymer with a narrow average molecular weight distribution and highsyndiotacticity; (2) an ethylene-styrene copolymer which has a highsyndiotactic chain composed of styrene structural units; (3) a1,3-cyclohexadiene polymer with high site regularity andstereoregularity; (4) a copolymer of 1,3-cyclohexadiene and anotherolefin monomer; and (5) a copolymer of another cyclic olefin.

That is, the present invention is as follows.

Firstly, the present invention is a polymerization catalyst compositionshown below.

[1] A polymerization catalyst composition, comprising:

(1) a metallocene complex represented by the general formula (I),including:

-   -   a central metal M which is a group III metal atom or a        lanthanoid metal atom;    -   a ligand Cp* bound to the central metal and including a        substituted or unsubstituted cyclopentadienyl derivative;    -   monoanionic ligands Q¹ and Q²; and    -   w neutral Lewis base L; and

(2) an ionic compound composed of a non-ligand anion and a cation:

where w represents an integer of 0 to 3.

[2] The polymerization catalyst composition according to [1], whereinthe central metal M contained in the metallocene complex is selectedfrom the group consisting of Scandium (Sc), Gadolinium (Gd), Yttrium(Y), Holmium (Ho), Lutetium (Lu), Erbium (Er), Dysprosium (Dy), Terbium(Tb), and Thulium (Tm).

[3] The polymerization catalyst composition according to [1], whereinthe ligand Cp* including a cyclopentadienyl derivative is anon-crosslinking type ligand.

[4] The polymerization catalyst composition according to [1], whereinthe cyclopentadienyl derivative contained in the ligand Cp* in themetallocene complex is tetramethyl(trimethylsilyl)cyclopentadienyl orpentamethylcyclopentadienyl.

[5] The polymerization catalyst composition according to [1], wherein atleast one of the monoanionic ligands Q¹ and Q² in the metallocenecomplex is a trimethylsilyl group.

[6] The polymerization catalyst composition according to [1], whereinthe neutral Lewis base L in the metallocene complex is tetrahydrofran.

Secondary, the present invention is the polymerization catalystcomposition used for the polymerization shown below in particular amongthe polymerization catalyst compositions indicated above.

[7] The polymerization catalyst composition according to any one of [1]to [6], which is used for an olefinmonomer polymerization.

[8] The polymerization catalyst composition according to [7], whereinthe olefin monomer is selected from the group consisting of anunsubstituted styrene, a substituted styrene, ethylene, α-olefin, diene,and norbornenes.

[9] The polymerization catalyst composition according to any one of [1]to [6], which is used for copolymerization of two or more kinds ofolefin monomers.

[10] The polymerization catalyst composition according to [9], whereinthe two or more kinds of olefin monomers are selected from the groupconsisting of an unsubstituted styrene, a substituted styrene, ethylene,α-olefin, diene, and norbornenes.

Thirdly, the present invention is a polymer or a copolymer shown below.

[11] A high syndiotactic polymer of a substituted or unsubstitutedstyrene, having Mw/Mn as an index of a molecular weight distribution of1.7 or less.

[12] The high syndiotactic polymer according to [11], whereinsyndiotacticity is 80 rrrr % or more in terms of a pentad indication.

[13] A high syndiotactic copolymer of a substituted or unsubstitutedstyrene and a substituted styrene, having Mw/Mn as an index of amolecular weight distribution of 1.7 or less.

[14] The high syndiotactic copolymer according to [13], wherein the highsyndiotactic copolymer has a syndiotacticity of 80 rrrr % or more interms of a pentad indication.

[15] A high syndiotactic copolymer of ethylene and a substituted orunsubstituted styrene.

[16] The high syndiotactic copolymer according to [15], wherein:

the high syndiotactic copolymer is a random copolymer, and has asyndiotacticity of a chain composed of styrene structural units of 98 r% or more in terms of a diad indication.

[17] The high syndiotactic copolymer according to [15], wherein:

the high syndiotactic copolymer is a block copolymer, and has asyndiotacticity of a styrene block chain of 80 rrrr % or more in termsof a pentad indication.

[18] The high syndiotactic copolymer according to any one of [15] to[17], having Mw/Mn as an index of a molecular weight distribution of 1.3or less.

[19] The high syndiotactic copolymer according to any one of [15] to[18], wherein a ratio of the styrene structural unit with respect to allthe structural units is 5 to 99 mol %.

[20]A polymer of a 1,3-cyclohexadiene, which has a ratio of a1,4-structural unit with respect to all the structural units of 90% ormore, and has a high cis-syndiotacticity.

[21] The polymer according to [20], wherein the polymer has acis-syndiotacticity of 70 rrrr % or more.

[22] A copolymer of 1,3-cyclohexadiene and a substituted orunsubstituted styrene, which has a ratio of a 1,4-structural unit withrespect to all structural units in the 1,3-cyclohexadiene of 90% ormore.

[23] The copolymer according to [22], which is a random copolymer andhas a syndiotacticity of a chain composed of styrene structural units of98 r % or more in terms of a diad indication.

[24] A copolymer of 1,3-cyclohexadiene and ethylene.

[25] The copolymer according to [24], wherein a ratio of a1,4-structural unit with respect to all the structural units of the1,3-cyclohexadiene is 90% or more.

[26] A copolymer of ethylene, norbornenes, and a substituted orunsubstituted styrene.

[27] The copolymer according to [26], wherein:

the copolymer is a random copolymer and has a syndiotacticity of a chaincomposed of styrene structural units of 98 r % or more in terms of adiad indication.

[28] A copolymer of dicyclopentadiene and ethylene, which has a numberaverage molecular weight of 100,000 or more.

[29] The copolymer according to [28], wherein a ratio of adicyclopentadiene structural unit with respect to all structural unitsis 10 mol % or more.

Fourthly, the present invention is a production method of polymer shownbelow.

[30] A production method of olefin copolymer, comprising: polymerizingan olefin monomer by using the polymerization catalyst compositionaccording to any one of [1] to [6].

[31] The production method according to [30], wherein the olefin monomeris one selected from the group consisting of a substituted styrene, anunsubstituted styrene, ethylene, diene, norbornenes, and α-olefin.

[32] A production method of olefin copolymer, comprising:

polymerizing two or more kinds of the olefin monomers by using thepolymerization catalyst composition according to any one of [1] to [6].

[33] The production method according to [32], wherein the two or morekinds of olefin monomers are selected from the group consisting of asubstituted styrene, an unsubstituted styrene, ethylene, diene,norbornenes, and α-olefin.

[34] The production method according to [30], wherein:

the olefin polymer is a substituted or unsubstituted styrene polymer;and

the olefin monomer is a substituted or unsubstituted styrene.

[35] The production method according to [34], wherein the substituted orunsubstituted styrene polymer is a high syndiotactic polymer.

[36] The production method according to [34], wherein the substituted orunsubstituted styrene polymer is the styrene polymer according to [11]or [12].

[37] The production method according to [32], wherein:

the olefin copolymer is a styrene copolymer; and

the olefin monomers are two or more kinds of the styrenes selected froma substituted styrene and an unsubstituted styrene.

[38] The production method according to [37], wherein the styrenecopolymer is a high syndiotactic copolymer.

[39] The production method according to [37], wherein the styrenecopolymer is the styrene copolymer according to [13] or [14].

[40] The production method according to [32], wherein:

the olefin copolymer is a copolymer of ethylene and a substituted orunsubstituted styrene; and

the olefin monomers are ethylene and a substituted or unsubstitutedstyrene.

[41] The production method according to [40], wherein the copolymer ofethylene and a substituted or unsubstituted styrene is the copolymer ofethylene and the substituted or unsubstituted styrene according to anyone of [15] to [19].

[42] The production method according to [30], wherein:

the olefin polymer is a 1,3-cyclohexadiene polymer; and

the olefin monomer is 1,3-cyclohexadiene.

[43] The production method according to [42], wherein the1,3-cyclohexadiene polymer is the 1,3-cyclohexadiene polymer accordingto [20] or [21].

[44] The production method according to [32], wherein:

the olefin copolymer is a copolymer of 1,3-cyclohexadiene and asubstituted or unsubstituted styrene; and

the olefin monomers are 1,3-cyclohexadiene and a substituted orunsubstituted styrene.

[45] The production method according to [44], wherein the copolymer of1,3-cyclohexadiene and a substituted or unsubstituted styrene is thecopolymer according to [22] or [23].

[46] The production method according to [32], wherein:

the olefin copolymer is a copolymer of 1,3-cyclohexadiene and ethylene;and

the olefin monomers are 1,3-cyclohexadiene and ethylene.

[47] The production method according to [46], wherein the copolymer of1,3-cyclohexadiene and ethylene is the copolymer according to [24] or[25].

[48] The production method according to [32], wherein:

the olefin copolymer is a copolymer of ethylene, norbornenes, and asubstituted or unsubstituted styrene; and

the olefin monomers are ethylene, norbornenes, and a substituted orunsubstituted styrene.

[49] The production method according to [48], wherein the copolymer isthe copolymer according to [26] or [27].

[50] The production method according to [32], wherein:

the olefin copolymer is a copolymer of dicyclopentadiene and ethylene;and

the olefin monomers are dicyclopentadiene and ethylene.

[51] The production method according to [50], wherein the copolymer ofdicyclopentadiene and ethylene is the copolymer according to [28] or[29].

[52] The production method according to [32], wherein:

the olefin copolymer is a copolymer of a substituted or unsubstitutedstyrene and a conjugated diene; and

the olefin monomers are a substituted or unsubstituted styrene and aconjugated diene.

Use of the catalyst composition of the present invention provides anovel polymerization reaction and a novel production method of a polymercompound.

Further, a syndiotactic styrene polymer with a narrow molecular weightdistribution, which is one of polymer compounds produced by using thecatalyst composition of the present invention, has additionally highquality while retaining original characteristics as sPS, whereby thesyndiotactic styrene polymer may be used as high-performance sPS.

Furthermore, an ethylene-styrene copolymer which is one of polymercompounds synthesized by using the catalyst composition of the presentinvention and which has a high syndiotactic chain composed of styrenestructural units, has additionally high processibility while retainingoriginal characteristics of sPS, whereby the ethylene-styrene copolymeris expected for a wide application compared to conventional sPS.

On the other hand, each of various cyclicolefin polymers (copolymers),which is one of polymer compounds produced by using the catalystcompound of the present invention, is expected for a wide application,for example, as an optical material.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a ¹³C-NMR spectrum chart of a styrene polymer of the presentinvention.

FIG. 2 shows ¹³C-NMR spectrum charts of an ethylene-styrene randomcopolymer of the present invention.

FIG. 3 shows enlarged parts of the spectrum charts of FIG. 2.

FIG. 4 shows ¹³C-NMR spectrum charts of polyethylene, poly(1-hexene),and a 1-hexene-ethylene copolymer, respectively.

FIG. 5 is a ¹³C-NMR spectrum chart of an ethylene-norbornene copolymer.

FIG. 6 shows ¹³C-NMR spectrum charts of 1,3-cyclohexadiene polymers,which were obtained in Examples 75, 76, 77, 78, and 82, respectively,and enlarged parts thereof (excluding Example 75).

FIG. 7 is an X-ray powder diffraction pattern of the 1,3-cyclohexadienepolymer obtained in Example 77.

FIG. 8 shows ¹H-NMR spectrum charts of copolymers of 1,3-cyclohexadieneand styrene, which were obtained in Examples 83 to 88, respectively.

FIG. 9 is a ¹³C-NMR spectrum chart of the copolymer of1,3-cyclohexadiene and styrene, which was obtained in Examples 85, andan enlarged parts thereof.

FIG. 10 shows ¹³C-NMR spectrum charts of the copolymers of1,3-cyclohexadiene and styrene, which were obtained in Examples 83 to88, respectively.

FIG. 11 is a graph showing GPC curves of the copolymers of1,3-cyclohexadiene and styrene, which were obtained in Examples 83 to88, respectively.

FIG. 12 shows ¹H-NMR spectrum charts of copolymers of 1,3-cyclohexadieneand ethylene, which were obtained in Examples 89 to 95, respectively.

FIG. 13 is a ¹³C-NMR spectrum chart of the copolymer of1,3-cyclohexadiene and ethylene, which was obtained in Example 92, andan enlarged parts thereof.

FIG. 14 shows ¹³C-NMR spectrum charts of the copolymers of1,3-cyclohexadiene and ethylene, which were obtained in Examples 89 and92, and enlarged parts thereof.

FIG. 15 is an ¹H-NMR spectrum chart of a terpolymer of ethylene,norbornene, and styrene, which was obtained in Example 99.

FIG. 16 is a ¹³C-NMR spectrum chart of the terpolymer of ethylene,norbornene, and styrene, which was obtained in Example 99.

FIG. 17 is a GPC curve of the terpolymer of ethylene, norbornene, andstyrene, which was obtained in Example 99.

FIG. 18 is an ¹H-NMR spectrum chart of a copolymer of dicyclopentadieneand ethylene, which was obtained in Example 102.

FIG. 19 is a ¹³C-NMR spectrum chart of the copolymer ofdicyclopentadiene and ethylene, which was obtained in Example 102.

FIG. 20 is a GPC curve of the copolymer of dicyclopentadiene andethylene, which was obtained in Example 102.

FIG. 21 is a ¹³C-NMR spectrum chart of a cyclohexadiene polymer, whichincludes a 1,4-structural unit and a 1,2-structural unit in a ratio ofabout 89:11.

FIG. 22 is a ¹³C-NMR spectrum chart of a styrene-isoprene copolymer (70mol % styrene).

BEST MODE FOR CARRYING OUT THE INVENTION

(Catalyst Composition of the Present Invention)

A catalyst composition of the present invention is characterized bycontaining a metallocene complex and an ionic compound. In addition, thecatalyst composition of the present invention may contain otherarbitrary components.

1. Metallocene Complex Contained in the Catalyst Composition of thePresent Invention

A metallocene complex (hereinafter, also referred to as “metallocenecomplex to be used in the present invention”) contained in the catalystcomposition of the present invention is a complex represented by thefollowing general formula (I). The complex is preferably a halfmetallocene complex.

In the general formula (I), M represents a central metal in themetallocene complex. The central metal M is a metal which belongs to agroup III metal or a lanthanoid metal, but is not particularly limited.A metallocene complex to be used in the present invention can be used asone component of a polymerization catalyst composition, so the centralmetal M may be suitably selected depending on the type of monomer to besubjected to polymerization, and the like.

In the case of polymerization of ethylene, for example, any of group IIImetals or lanthanoid metals may be used, and, for example, any ofScandium (Sc), Gadolinium (Gd), Yttrium (Y), Holmium (Ho), Lutetium(Lu), Erbium (Er), Dysprosium (Dy), Terbium (Tb), and Thulium (Tm) maybe selected as shown in the following Examples.

In the case of polymerization of styrene, any of group III metals orlanthanoid metals may be used, and any of Sc, Gd, Y, and Lu may beselected as shown in the following Examples.

Cp* in the general formula (I) represents a ligand containing acyclopentadienyl derivative, and binds to the central metal M with a Hbond. The ligand is preferably a non-crosslinking type ligand. Here, theterm “non-crosslinking type ligand” refers to a ligand which has acyclopentadienyl derivative bound to the central metal M with a π bondand has no ligand atom or ligand group other than the cyclopentadienylderivative.

Examples of the cyclopentadienyl derivative in Cp* include acyclopendadienyl ring and a condensed ring containing cyclopentadienyl(which includes, but not limited to, an indenyl ring and a fluorenylring). The most preferable cyclopentadienyl derivative is acyclopentadienyl ring.

A cyclopentadienyl ring is represented by the composition formulaC₅H_(5-x)R_(x). In the formula, x represents an integer of 0 to 5. Eachof R's independently represents a hydrocarbyl group, a substitutedhydrocarbyl group, or a metalloid group which is substituted by ahydrocarbyl group.

The hydrocarbyl group is preferably a hydrocarbyl group having 1 to 20carbon atoms, more preferably a C1-20 (preferably C1-10, more preferablyC1-6)alkyl group, phenyl group, benzyl group, or the like, and mostpreferably a methyl group.

A hydrocarbyl group in the substituted hydrocarbyl group is the same asthe above-mentioned hydrocarbyl group. The term “substituted hydrocarbylgroup” refers to a hydrocarbyl group in which at least one hydrogen atomis substituted by any of a halogen atom, an amide group, a phosphidegroup, an alkoxy group, an aryloxy group, and the like.

Examples of a metalloid in the metalloid group which is substituted by ahydrocarbyl group include Germyl (Ge), Stanyl (Sn), and Silyl (Si).Further, a hydrocarbyl group as a substituent in a metalloid group isthe same as the above-mentioned hydrocarbyl group. The number ofhydrocarbyl group for substitution is determined depending on the typeof metalloid (in the case of a silyl group, for example, the number ofhydrocarbyl group for substitution is 3).

At least one of R's in the cyclopentadienyl ring is preferably ametalloid group (more preferably a silyl group) which has a hydrocarbylgroup as a substituent, and more preferably a trimethylsilyl group.

Specific examples of preferable cyclopentadienyl ring include, but notlimited to, compounds represented by the following formulae.

The cyclopentadienyl derivative in the ligand Cp* may be any of anindenyl ring (composition formula: C₉H_(7-x)R_(x)), a tetrahydroindenylring (composition formula: C₉H_(11-x)R_(x)), and the like. Here, Rrepresents the same R as in the above-mentioned cyclopentadienyl ring,and X represents an integer of 0 to 7 or 0 to 11.

The cyclopentadienyl derivative in the ligand Cp* may be any of afluorenyl ring (composition formula: C₁₃H_(9-x)R_(x)), an octafluorenylring (composition formula: C₁₃H_(17-x)R_(x)), and the like. Here, Rrepresents the same R as in the above-mentioned cyclopentadienyl ring,and X represents an integer of 0 to 9 or 0 to 17.

In a complex represented by the general formula (I), which is to be usedin the present invention, Q¹ and Q² are monoanionic ligands identical toor different from each other. Examples of the monoanionic ligandinclude, but not limited to, 1) a hydrido, 2) a halide, 3) a substitutedor unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, 4) analkoxy group or aryloxy group, 5) an amide group, and 6) a phosphinogroup.

Further, Q¹ and Q² may be bound to each other, or form a so-calleddianionic ligand in combination. Examples of the dianionic ligandinclude alkylidene, diene, a cyclometalled hydrocarbyl group, and abidentate chelate ligand.

The halide may be any of the chloride, bromide, fluoride, and iodide.

Preferable examples of the hydrocarbyl group having 1 to 20 carbon atomsinclude: an alkyl group such as a methyl group, an ethyl group, a propylgroup, a butyl group, an amyl group, an isoamyl group, a hexyl group, anisobutyl group, a heptyl group, an octyl group, a nonyl group, a decylgroup, a cetyl group, or a 2-ethylhexyl group; a unsubstitutedhydrocarbyl group such as a phenyl group or a benzyl group; and asubstituted hydrocarbyl group such as a substituted benzyl group, atrialkylsilylmethyl group, or a bis(trialkylsilyl)methyl group.Preferable examples of the hydrocarbyl group include a substituted orunsubstituted benzyl group and a trialkylsilylmethyl group. Morepreferable examples of the hydrocarbyl group include anortho-dimethylaminobenzyl group or trimethylsilylmethyl group.

Preferable examples of the alkoxy group or aryloxy group include amethoxy group or a substituted or unsubstituted phenoxy group.

Preferable examples of the amide group include a dimethylamide group, adiethylamide group, a methylethylamide group, a di-t-butylamide group, adiisopropylamide group, and an unsubstituted or substituteddiphenylamide group.

Preferable examples of the phosphino group include a diphenylphosphinogroup, a dicyclohexylphosphino group, a diethylphosphino group, and adimethylphosphino group.

Preferable examples of the alkylidene include methylidene, ethylidene,and propylidene.

Preferable examples of the cyclometalled hydrocarbyl group includepropylene, butylene, pentylene, hexylene, and octylene.

Preferable examples of the diene include 1,3-butadiene, 1,3-pentadiene,1,4-pentadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene,2,4-dimethyl-1,3-pentadiene, 2-methyl-1,3-hexadiene, and 2,4-hexadiene.

In the complex represented by the general formula (I), which is to beused in the present invention, L represents a neutral Lewis base.Examples of the neutral Lewis base include tetrahydrofran, diethylether,dimethylaniline, trimethylphosphine, and lithium chloride.

Further, L may bind to Q¹ and/or Q² to form a so-called multidentateligand.

w of L_(w) in the general formula (I) represents the number of neutralLewis base L. w represents an integer of 0 to 3, preferably 0 to 1.

A metallocene complex to be used in the present invention may besynthesized according to a known method, for example, the methoddescribed in (1) Tardif, O.; Nishiura, M.; Hou, Z. M. Organometallics22, 1171, (2003) or (2) Hultzsch, K. C.; Spaniol, T. P.; Okuda, J.Angew. Chem. Int. Ed, 38, 227, (1999).

Further, specific examples of production methods of those complex aredescribed in the following reference examples.

2. Ionic Compound Contained in the Catalyst Composition of the PresentInvention

As described above, the catalyst composition of the present inventioncontains an ionic compound. Here, the term “ionic compound” includes anionic compound composed of an coordinated anion and a cation. The ioniccompound is combined with the metallocene complex and thus allows themetallocene complex to exert an activity as a polymerization catalyst. Apossible mechanism may involve a reaction of an ionic compound with ametallocene complex to produce a cationic complex (active species).

An example of the uncoordinated anion which is a component of an ioniccompound preferably includes a tetravalent boron anion. Examples of thetetravalent boron anion include tetra(phenyl)borate,tetrakis(monofluorophenyl)borate, tetrakis(difluorophenyl)borate,tetrakis(trifluorophenyl)borate, tetrakis(trifluorophenyl)borate,tetrakis(pentafluorophenyl)borate,tetrakis(tetrafluoromethylphenyl)borate, tetra(tolyl)borate,tetra(xylyl)borate, (tripheyl, pentafluorophenyl)borate,[tris(pentafluorophenyl), phenyl]borate, andtridecahydride-7,8-dicarbaundecaborate.

Of those uncoordinated anions, tetrakis(pentafluorophenyl)borate ispreferable.

Examples of the cation which is a component of an ionic compound includea carbonium cation, an oxonium cation, an ammonium cation, a phosphoniumcation, a cycloheptatrienyl cation, and a ferrocenium cation having atransition metal.

A specific example of the carbonium cation includes a trisubstitutedcarbonium cation such as a triphenylcarbonium cation or atri-substituted phenylcarbonium cation. Specific examples of thetri-substituted phenylcarbonium cation include atri(methylphenyl)carbonium cation and a tri(dimethylphenyl)carboniumcation.

Specific examples of the ammonium cation include: a trialkylammoniumcation such as trimethylammonium cation, a triethylammonium cation, atripropylammounium cation, a tributylammonium cation, ortri(n-butyl)ammonium cation; an N,N-dialkylanilinium cation such as anN,N-dimethylanilinium cation, an N,N-diethylanilinium cation, or anN,N-2,4,6-pentamethylanilinium cation; and a dialkylammonium cation suchas a di(isopropyl)ammonium cation or a dicyclohexylammonium cation.

A specific example of the phosphonium cation includes atriarylphosphonium cation such as a triphenylphosphonium cation, atri(methylphenyl)phosphonium cation, or a tri(dimethylphenyl)phosphoniumcation.

Of those cations, anilinium cation or carbonium cation is preferable,and a triphenylcarbonium cation is more preferable.

That is, the ionic compound contained in the catalyst composition of thepresent invention may be a compound obtained by combining a coordinatedanion and a cation, each of which is selected from the above-mentionedcoordinated anions and cations, respectively.

Preferable examples of the ionic compound include triphenylcarboniumtetrakis(pentafluorophenyl)borate, triphenylcarboniumtetrakis(tetrafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, and1,1′-dimethylferroceniumtetrakis(pentafluorophenyl)borate. One kind ofthe ionic compound may be used, or two or more kinds of them can be usedin combination.

Of those ionic compounds, an example of a particularly preferable ioniccompound includes triphenylcarbonium tetrakis(pentafluorophenyl)borate.

Further, for example, B(C₆F₅)₃ or Al(C₆F₅)₃, which is a Lewis acidcapable of producing a cationic metal transition compound by reactionwith a transition metal compound, may be used as an ionic compound, andany of those compounds may be used in combination with any of theabove-mentioned ionic compounds.

In addition, a combination of an alkylaluminum compound (e.g.,aluminoxane, or preferably MAO or MMAO) or an alkylaluminum compound anda borate compound may be used as an ionic compound, and such an ioniccompound may be used in combination with another ionic compound. Inparticular, when a monoanionic ligand Q of the above-mentioned complexrepresented by the general formula (I) to be used in the presentinvention is other than an alkyl and a hydrido (for example, the ligandis a halogen), it is thought to be preferable to use a combination of analkylaluminum compound or an alkylaluminum compound and a boratecompound.

3. Other Arbitrary Components Contained in the Catalyst Composition ofthe Present Invention

The catalyst composition of the present invention may contain otherarbitrary components in addition to the metallocene complex and theionic compound. Examples of the arbitrary components include analkylaluminum compound, a silane compound, and hydrogen.

An example of the alkylaluminum compound includes an organic aluminumcompound which is generally used with a metallocene polymerizationcatalyst and referred to as “aluminoxane (almoxane)”.

An example of the organic aluminum compound includes methylalminoxane(MAO).

An example of the silane compound includes phenylsilane.

4. Catalyst Composition of the Present Invention

As described above, the catalyst composition of the present invention ischaracterized by containing the above-mentioned metallocene compound andionic compound. In the catalyst composition of the present invention, amolar ratio of the ionic compound to the metallocene compound variesdepending on the types of the complex and the ionic compound.

For example, in the case where the ionic compound is composed ofcarbonium cations and borate anions (for example, the ionic compound is[Ph₃C][B(C₆F₅)₄]), the above-mentioned molar ratio is preferably 0.5 to1, and in the case of MAO or the like, the molar ratio is preferablyabout 300 to 4,000.

It is thought that an ionic compound ionizes, specifically, cationizes ametallocene complex to make the metallocene complex be a catalyst activespecies. Therefore, if the ionic compound has the ratio not more thanthat described above, the compound is unable to sufficiently activatethe metallocene complex.

On the other hand, if an ionic compound composed of carbonium ions andborate anions exists in an excess amount, there is a fear that thecompound may react with a monomer which is to be subjected to apolymerization reaction.

In general, Lewis acid L is thought to inhibit coordination of olefinmonomer to an active center, so a complex represented by the generalformula (I) in which w is 0 may be referred to as a preferable complexto be used in the present invention.

The catalyst composition of the present invention may be used as apolymerization catalyst composition (particularly an additionpolymerization catalyst composition).

For example, the catalyst composition can be used as a polymerizationcatalyst composition by 1) providing a composition including respectivecomponents (such as a metallocene complex and an ionic compound) into apolymerization reaction system or 2) providing respective componentsseparately to the polymerization reaction system to compose acomposition in the reaction system.

In the item 1), the phrase “providing a composition” includes providinga metallocene complex (active species) which has been activated by areaction with an ionic compound.

As described above, the catalyst composition of the present inventionmay be used as a polymerization catalyst composition in polymerizationreactions of various kinds of monomers. Examples of the polymerizationreaction on which the catalyst composition of the present invention mayhave an effect as a catalyst, include a polymerization reaction ofarbitrary monomer compound which is known to have an additionpolymerization activity. Specific examples of the polymerizationreaction include polymerization reactions of an olefin-based monomer, anepoxy-based monomer, an isocyanate-based monomer, a lactone-basedmonomer, a lactide-based monomer, a cyclic carbonate-based monomer, andan alkyne-based monomer, respectively. Specific examples of thepolymerization reaction preferably include a polymerization reaction ofan olefin-based monomer, and particularly preferably polymerizationreactions of α-olefin, styrene, ethylene, diene, and cyclic olefins(including norbornenes such as 2-norbornene and dicyclopentadiene, andcyclohexadiene), respectively.

Here, an example of the diene that is an olefin-based monomer includes acyclic diene such as 1,3-butadiene, 1,3-pentadiene, 1,4-pentadiene,1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene,2,4-dimethyl-1,3-pentadiene, 2-methyl-1,3-hexadiene, 2,4-hexadiene, orcyclohexadiene.

Further, the polymerization catalyst composition of the presentinvention can be used as a polymerization catalyst composition in acopolymerization reaction as well as a homopolymerization reaction. Amonomer to be subjected to copolymerization may at least be capable ofaddition polymerization. Two or more olefin monomers are preferablyused, and particularly preferably two or more of monomers selected fromthe group consisting of an α-olefin, a substituted or unsubstitutedstyrene, ethylene, diene, and a cyclic olefin are used.

(Polymer Compound of the Present Invention)

An embodiment of the polymer compound of the present invention is a highsyndiotactic polymer of a substituted or unsubstituted styrene, or ahigh syndiotactic copolymer of two or more kinds of styrene selectedfrom the group consisting of a substituted or unsubstituted styrene,which is characterized by having a narrow molecular weight distribution(hereinafter, they may be referred to as “styrene polymer of the presentinvention” and “styrene copolymer of the present invention”,respectively, and both of them may be referred to as “styrene polymer(copolymer) of the present invention”, collectively).

An embodiment of the polymer compound of the present invention is anethylene-styrene copolymer, which is characterized in that its chaincomposed of styrene structural units has high syndiotacticstereoregularity (hereinafter, also referred to as “ethylene-styrenecopolymer of the present invention”).

An embodiment of the polymer compound of the present invention is a1,3-cyclohexadiene polymer, which is characterized by having a highratio of 1,4-structural unit with respect to the total structural unitsand being a high cis-syndiotactic polymer (hereinafter, also referred toas “CHD polymer of the present invention”).

An embodiment of the polymer compound of the present invention is acopolymer of 1,3-cyclohexadiene and another olefin. An example of thecopolymer includes a copolymer of 1,3-cyclohexadiene and a substitutedor unsubstituted styrene, which is characterized by having a high ratioof 1,4-structural unit with respect to the total structural units of1,3-cyclohexadiene (hereinafter, also referred to as “CHD-ST copolymerof the present invention”). Another example of the polymer compound ofthe present invention includes a copolymer of 1,3-cyclohexadiene andethylene (hereinafter, also referred to as “CHD-ET copolymer of thepresent invention”).

An embodiment of the polymer compound of the present invention is acopolymer of norbornenes, ethylene, and a substituted or unsubstitutedstyrene (hereinafter, also referred to as “NBE-ET-ST copolymer of thepresent invention”).

An embodiment of the polymer compound of the present invention is acopolymer of dicyclopentadiene and ethylene, which is characterized byhaving a specific molecular weight (hereinafter, also referred to as a“DCPD-ET copolymer of the present invention”).

1. Styrene Polymer or Styrene Copolymer of the Present Invention

The styrene polymer or styrene copolymer (styrene polymer (copolymer))of the present invention is a polymer including a styrene (with orwithout a substituent (R)_(n) on the phenyl ring) repetitive unit, whichis represented by the following formula (A). The repetitive unitrepresented by the formula (A) is generally repeated with a head to tailbond. The repetitive unit represented by the formula (A) in the styrenepolymer (copolymer) of the present invention may be one kind (homopolymer) or two or more kinds (copolymer).

R on the phenyl ring in the formula (A) is an arbitrary substituent oratom. Examples of R include a halogen atom, an alkyl group having 1 to 4carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylsilylgroup, and a carboxyalkyl group.

A phenyl ring of a styrene structural unit in the styrene polymer(copolymer) of the present invention has R in a number denoted by n. nis preferably 0 to 3, and more preferably 0 or 1. The most preferablecase is that n is 0 or that n is 1, and R binds to a phenyl ring carbonat para position with respect to the phenyl ring carbon binding to apolymer main chain.

Examples of the substituent or atom represented by (R)_(n) include, butnot limited to, the following ones.

1) analkylsuchas p-methyl, m-methyl, o-methyl, 2,4-dimethyl,2,5-dimethyl, 3,4-dimethyl, 3,5-dimethyl, or p-tertiarybutyl;

2) a halogen such as p-chloro, m-chloro, o-chloro, p-bromo, m-bromo,o-bromo, p-fluoro, m-fluoro, o-fluoro, or o-methyl-p-fluoro;

3) a halogen-substituted alkyl such as p-chloromethyl, m-chloromethyl,or o-chloromethyl;

4) an alkoxy such as p-methoxy, m-methoxy, o-methoxy, p-ethoxy,m-ethoxy, or o-ethoxy;

5) a carboxyalkyl such as p-carboxymethyl, m-carboxymethyl, oro-carboxymethyl;

6) an alkylsilyl such as p-trimethylsilyl.

The styrene polymer (copolymer) of the present invention is a polymerwith stereoregularity, and also is a high syndiotactic polymer. Here,the term “high syndiotactic” means that a ratio that phenyl rings inadjacent repetitive units represented by the formula (A) are alternatelyarranged with respect to the plane composed of a polymer main chain (theratio is referred to as “syndiotacticity”), is high.

Syndiotacticity of the styrene polymer (copolymer) of the presentinvention is 80 rrrr % or higher in terms of a pentad indication(preferably 85 rrrr %, more preferably 90 rrrr %, particularlypreferably 95 rrrr %, and most preferably 99 rrrr %). Thesyndiotacticity may be calculated from measurement data of NMR(particularly ¹³C-NMR) of the styrene polymer (copolymer) of the presentinvention. Specific description of the calculation is made in theExamples described below.

The styrene polymer (copolymer) of the present invention ischaracterized by having a narrow molecular weight distribution. Here,the term “molecular weight distribution” refers to a measurement value(Mw/Mn) obtained by a GPC method (where a measurement is performed byusing polystyrene as a reference material and 1,2-dichlorobenzene as aneluate at 145° C.). The molecular weight distribution can be measured byusing a GPC measurement device (TOSOH HLC 8121 GPC/HT), for example.

Here, the term “narrow molecular weight distribution” means that Mw/Mnis generally 1.7 or less, preferably 1.6 or less, more preferably 1.5 orless, and most preferably 1.4 or less.

A number average molecular weight of the styrene polymer (copolymer) ofthe present invention is arbitrary. A number average molecular weight ofunsubstituted styrene polymer is preferably 0.4×10⁴ or more, morepreferably 8.5×10⁴ or more, still more preferably 20.0×10⁴ or more, andmost preferably 25.0×10⁴ or more.

A melting point of polystyrene of the present invention is generally260° C. or higher. The melting point can be measured by a differentialscanning calorimetry (DSC) method.

The styrene polymer (copolymer) of the present invention hascharacteristics similar to those of a conventionally known syndiotacticstyrene polymer (copolymer) (sPS). That is, the styrene polymer(copolymer) of the present invention has characteristics such as a highmelting point, heat resistance, chemical resistance, and dimensionstability, and thus may be used as any of various kinds of engineerplastics. Further, the styrene polymer (copolymer) of the presentinvention is expected to be used as an engineer plastic havingadditional high-quality because of its physical properties, that is, asharp molecular weight distribution.

2. Ethylene-Styrene Copolymer of the Present Invention

The ethylene-styrene copolymer of the present invention is a copolymerhaving a structural unit derived from styrene, which is represented bythe following formula (A), and a structural unit derived from ethylene,which is represented by the formula (B). The structural unit representedby the formula (A) may be one kind or two or more kinds.

Here, R and n in the formula (A) are similar to R and n in therepetitive unit represented by the formula (A) described earlier in thepart of the styrene polymer (copolymer), respectively.

In the ethylene-styrene copolymer of the present invention, structuralunits represented by the formulae (A) and (B) may each be arranged in anarbitrary order. In other words, each of those structural units may bearranged in a random manner, or with a certain regularity (for example,structural units represented by the formulae (A) and (B) are arranged inan alternate manner, in a successive manner to some degree, or in otherdetermined order). Therefore, the ethylene-styrene copolymer of thepresent invention may be any of a random copolymer, an alternatecopolymer, a block copolymer, and other sequence-defined copolymer. Theethylene-styrene copolymer of the present invention is preferably arandom copolymer or block copolymer.

The ethylene-styrene copolymer of the present invention is characterizedby having stereoregularity. That is, when structural units in thecopolymer, which are represented by the formula (A), are successive, thecopolymer is characterized by having a high ratio (syndiotacticity) ofphenyl rings in the repetitive structural units represented by theformula (A) alternately arranged with respect to the plane composed of apolymer main chain.

Here, the term “syndiotacticity of an ethylene-styrene copolymer, whichis a random copolymer” refers to a ratio of diad (represented by r %)which is a syndiotactic sequence (sequence in which a phenyl group isarranged in an alternate manner with respect to a polymer main chain)among all of the two successive units (diad) of structural unitrepresented by the formula (A) in the copolymer.

The ethylene-styrene copolymer of the present invention, which is arandom copolymer, has syndiotacticity of chain composed of structuralunits represented by the formula (A) of 60 r % or more, preferably 80 r% or more, and more preferably 98 r % or more in terms of a diadindication.

The syndiotacticity of the ethylene-styrene copolymer, which is a randomcopolymer, can be calculated from ¹³C-NMR spectrum. Specific descriptionof the calculation is made in the Examples described below.

On the other hand, the term “syndiotacticity of an ethylene-styrenecopolymer, which is a block copolymer” refers to a ratio of pentad(represented by rrrr %) which is a syndiotactic sequence (sequence inwhich a phenyl group is arranged in an alternate manner with respect toa polymer main chain) among all of the five successive units (pentad) ina styrene block chain (block chain in which a structural unitrepresented by the formula (A) is repetitive) in the copolymer.

The ethylene-styrene copolymer of the present invention, which is ablock copolymer, has syndiotacticity of styrene block chain of 80 rrrr%, preferably 85 rrrr %, and more preferably 90 rrrr %, particularlypreferably 95 rrrr %, and most preferably 99 rrr % or more in terms of apentad indication.

The syndiotacticity of the ethylene-styrene copolymer, which is a blockcopolymer, can be determined in the same way as that of theabove-mentioned styrene polymer (copolymer) of the present invention(that is, the syndiotacticity can be determined from NMR spectrum).

Contents of the structural unit represented by the formula (A) and thestructural unit represented by the formula (B) which are present in theethylene-styrene copolymer of the present invention are arbitrary. Forexample, of all structural units, a content of the structural unitrepresented by the formula (A) may be 5 to 99 mol % in a molar ratio.

When a content of the structural unit represented by the formula (A)increases, characteristics in which a sequence of the structural unitrepresented by the formula (A) (structural unit derived from styrene)has high stereoregularity (the sequence of high syndiotacticity), whichis a characteristic of the ethylene-styrene copolymer of the presentinvention, may be effectively exerted. In other words, an increase inthe content of the structural unit can provide the ethylene-styrenecopolymer of the present invention with characteristics of a highsyndiotactic polystyrene, such as heat resistance, chemical resistance,and dimension stability.

Meanwhile, the ethylene-styrene copolymer of the present inventionincludes a structural unit derived from ethylene and represented by theformula (B), so difficulties in forming, which have been involved in aconventional syndiotactic polystyrene, are reduced.

A molecular weight distribution of the ethylene-styrene copolymer of thepresent invention is arbitrary, but the copolymer may have a relativelynarrow molecular weight distribution. Here, the term “molecular weightdistribution” refers to a measurement value (Mw/Mn) obtained by a GPCmethod (where a measurement is performed by using polystyrene as areference material and 1,2-dichlorobenzene as an eluate at 145° C.). Themolecular weight distribution may be measured by using a GPC measurementdevice (TOSOH HLC 8121 GPC/HT), for example.

In general, the ethylene-styrene copolymer of the present invention hasMw/Mn, as an index of the molecular weight distribution, of 4.0 or less,preferably 2.0 or less, or more preferably 1.3 or less.

A number average molecular weight of the ethylene-styrene copolymer ofthe present invention is arbitrary. A number average molecular weight ofethylene-unsubstituted styrene copolymer is generally 1.0×10⁴ or more,preferably 8.0×10⁴ or more, or more preferably 50.0×10⁴ or more.

A melting point of the ethylene-styrene copolymer of the presentinvention varies depending on the structure of structural unit derivedfrom styrene, a ratio between the structural unit derived from styreneand the structural unit derived from ethylene, and the like. Theethylene-styrene copolymer of the present invention having a meltingpoint of 200° C. or higher is expected to have characteristics similarto those of a conventionally known sPS, such as heat resistance,chemical resistance, and dimension stability. The melting point here isa melting point measured by a differential scanning calorimetry (DSC)method.

3. Conjugate Diene-Styrene Copolymer Produced by the Production Methodof the Present Invention

A conjugate diene-styrene copolymer produced by the production method ofthe present invention will be described by using an isoprene-styrenecopolymer as an example. The isoprene-styrene copolymer produced by theproduction method of the present invention (hereinafter, referred to as“isoprene-styrene copolymer of the present invention”) is a copolymerhaving a structural unit derived from styrene and represented by thefollowing formula (A) and at least one kind of structural units derivedfrom isoprene, which are represented by the formulae (C1) to (C4). Thestructural unit represented by the formula (A) may be one kind or two ormore kinds. A major unit in the structural units derived from isopreneis a structural unit represented by (C1) (for example, a content of C1is 60% or more of all structural units derived from isoprene)

In the isoprene-styrene copolymer of the present invention, structuralunits represented by the formulae (A) and (C1) to (C4) may each bearranged in an arbitrary order. In other words, each of those structuralunits may be arranged in a random manner, or with a certain regularity.Therefore, the isoprene-styrene copolymer of the present invention maybe any of a random copolymer, an alternate copolymer, a block copolymer,and other sequence-defined copolymer. The isoprene-styrene copolymer ofthe present invention is preferably a random copolymer or blockcopolymer, and more preferably a random copolymer.

The isoprene-styrene copolymer of the present invention preferably hasstereoregularity. That is, it is preferable that when the structuralunits represented by the formula (A) in the copolymer are successive, aratio (syndiotacticity) that phenyl rings in the successive structuralunits represented by the formula (A) alternately arranged with respectto the plane composed of a polymer main chain, is high.

On the other hand, tacticity of any of structural units represented bythe formulae (C1) to (C4) is not particularly limited. For example, thetacticity is atactic.

Of all two successive units (diad) of structural unit represented by theformula (A) in the isoprene-styrene copolymer, which is a randomcopolymer, a ratio of diad (represented by r %) which is a syndiotacticsequence is 60 r % or more, preferably 80 r % or more, and morepreferably 98 r % or more.

The syndiotacticity of the isoprene-styrene copolymer, which is a randomcopolymer, can be calculated from ¹³C-NMR spectrum.

Ratios of the structural unit represented by the formula (A) and thestructural units represented by the formulae (C1) to (C4), all of whichare present in the isoprene-styrene copolymer of the present invention,are arbitrary. For example, of all structural units, a molar ratio ofthe structural unit represented by the formula (A) may be 5 to 90 mol %.

A molecular weight distribution of the isoprene-styrene copolymer of thepresent invention is arbitrary. For example, the isoprene-styrenecopolymer has Mw/Mn as an index of the molecular weight distribution of1.8 or less, and preferably 1.2 or less. The molecular weightdistribution is measured by the same method as the method used formeasurement of the molecular weight distribution of the above-mentionedethylene-styrene copolymer.

A number average molecular weight of the isoprene-styrene copolymer ofthe present invention is arbitrary. In the case of anisoprene-unsubstituted styrene copolymer, the number average molecularweight is generally 30,000 or more, and preferably 100,000 or more.

A melting point of the isoprene-styrene copolymer of the presentinvention varies depending on the structure of structural unit derivedfrom styrene, ratios of the respective structural units, and the like,but the melting point is generally about 250° C.

3. 1,3-cyclohexadiene Polymer of the Present Invention

The 1,3-cyclohexadiene polymer (CHD polymer) of the present invention ischaracterized by having a high ratio of 1,4-structural unit with respectto all structural units therein. That is, as shown in the followingformula, the CHD polymer may include a 1,4-structural unit and a1,2-structural unit depending on the binding manner. The CHD polymer ofthe present invention is characterized by having a high ratio of the1,4-structural unit with respect to all structural units therein. Theterm “high ratio of 1,4-structural unit” means that {the number of1,4-structural unit/(the number of 1,4-structural unit+the number of1,2-structural unit)} is 80% or more, preferably 90% or more, morepreferably 95% or more, and still more preferably 99% or more.

The ratio of 1,4-structural unit with respect to all structural units inthe CHD polymer of the present invention can be determined from ¹³C-NMRspectrum data. That is, a peak of olefin carbon of 1,2-structure unit inthe CHD polymer is observed at around 128 ppm while a peak of olefincarbon of 1,4-structural unit is observed at around 132 ppm (see FIG.21). Thus, peak areas may be compared with each other to obtain theratio of 1,4-structural unit.

The CHD polymer of the present invention is characterized by having ahigh ratio of 1,4-structural unit with respect to all structural units,and further, by being a polymer with stereoregularity and a highcis-syndiotactic polymer.

That is, two successive units (diad) of 1,4-structural unit generallypresent in a CHD polymer may be any of the following four geometricisomer. In contrast, the CHD polymer of the present invention ischaracterized by having a high ratio of cis-syndiotactic two successiveunits (the ratio is referred to as “cis-syndiotacticity”) with respectto all two successive units of 1,4-structural unit therein.

Specifically, the cis-syndiotacticity of the CHD polymer of the presentinvention is generally 70 rrrr % or more, preferably 80 rrrr % or more,more preferably 90 rrrr % or more, and most preferably 99 rrrr % ormore.

The cis-syndiotacticity of the CHD polymer of the present invention canbe measured by analyzing ¹³C-NMR spectrum or an X-ray powder diffractionpattern.

As shown in the enlarged diagrams in FIG. 6 and FIG. 21, it is knownthat in the ¹³C-NMR spectrum of 1,3-cyclohexadine polymer, a signal oftertiary carbon which links a 1,3-cyclohexadiene unit is observed as amultipeak at around 39 to 41 ppm. Further, a peak at around 40.7 ppm isthought to be an all-trans structure, and other peaks are thought to beall-cis or cis-trans structures (see Z. Sharaby et al., Macromolecules,15, 1167-1173 (1982)).

Further, as described in Non-patent document 7 (Journal of PolymerScience: Part B: Polymer Physics, Vol. 39, 973-978 (2001)), X-ray powderdiffraction patterns of powders of cis-syndiotactic polymer andcis-isotactic polymer are the same, with the cis-syndiotactic polymerhaving more stable structure than the cis-isotactic polymer. Therefore,it is thought that annealing of the cis-isotactic polymer results in achange in the structure and further change in a diffraction pattern,while annealing of the cis-syndiotactic polymer does not cause a changein the structure and further change in a diffraction pattern (thosephenomena will be described in detail in Non-patent document 7).

As shown in FIG. 7, in a powder of the CHD polymer (polymer obtained inExample 72) of the present invention, its X-ray powder diffractionpattern does not change before and after being subjected to annealing(at 227° C., under argon atmosphere, heating for 30 minutes).

In view of the foregoing, a peak at 39.9 ppm is attributed to rrrr(cis-syndiotactic), and a peak at 40.1 ppm is attributed to rr.

The cis-syndiotacticity of the CHD polymer of the present invention canbe controlled by arbitrarily selecting the kind of ligand of ametallocene complex contained in a catalyst composition to be used inthe production of the polymer (described later), kind of central metal,kinds of anion and cation of the ionic compound, reaction temperature,reaction solvent, and the like.

A molecular weight distribution of the CHD polymer of the presentinvention is not particularly limited. In general, the CHD polymer hasMw/Mn, as an index of the molecular weight distribution, of 2.6 or less,and preferably 2.0 or less.

Here, the term “molecular weight distribution” refers to a measurementvalue (Mw/Mn) obtained by a GPC method (where a measurement is performedby using polystyrene as a reference material and 1,2-dichlorobenzene asan eluate at 145° C.). The molecular weight distribution may be measuredby using a GPC measurement device (TOSOH HLC 8121 GPC/HT), for example.

A molecular weight of the CHD polymer of the present invention is notparticularly limited, but the number average molecular weight of the CHDpolymer is preferably 7,000 or less. Further, a lower limit is notparticularly limited, but is preferably 1,000 or more.

The number average molecular weight may be measured by the same GPCmethod as that used for the molecular weight distribution.

The CHD polymer of the present invention generally has a melting point.The temperature at the melting point is not particularly limited, but isgenerally about 220 to 250° C. The melting point here is a melting pointmeasured by a differential scanning calorimetry (DSC) method.

4. Copolymer of 1,3-cyclohexadiene and Substituted or UnsubstitutedStyrene (Chd-ST Copolymer) of the Present Invention

The copolymer of 1,3-cyclohexadiene and substituted or unsubstitutedstyrene of the present invention is a polymer including a1,3-cyclohexadiene structural unit and a styrene structural unit(preferably consisting of both of the units). Here, a content of the1,3-cyclohexadiene structural unit in the CHD-ST copolymer of thepresent invention can be arbitrarily selected and controlled in a rangeof about 0 mol % to 100 mol %.

The content can be measured by means of ¹H-NMR. For example, as shown inFIG. 8, a peak derived from olefin hydrogen of cyclohexadiene structuralunit is observed at around 5.2 to 6.0 ppm, while a peak of aromatichydrogen of styrene structural unit is observed at around 6.7 to 7.4ppm. Thus, the content may be determined from the ratio between both ofthe peaks.

In production of a CHD-ST copolymer, the content may be controlled byadjusting ratios of the respective monomers as raw materials.

As described above, the CHD-ST copolymer of the present inventionincludes a 1,3-cyclohexadiene structural unit and a styrene structuralunit, and both the structural units may be arranged in an arbitraryorder. In other words, each of those structural units may be arranged ina random manner, or with a certain regularity (for example, both thestructural units are arranged in an alternate manner, in a successivemanner to some degree, or in other determined order). Therefore, theCHD-ST copolymer of the present invention may be any of a randomcopolymer, an alternate copolymer, a block copolymer, and othersequence-defined copolymer. The CHD-ST copolymer of the presentinvention is preferably a random copolymer or block copolymer, and morepreferably a random copolymer.

The CHD-ST copolymer of the present invention is characterized by havinga high ratio of a 1,4-structural unit with respect to all structuralunits of 1,3-cyclohexadiene which is contained in the copolymer. A ratioof the 1,4-structural unit is generally 80% or more, preferably 90% ormore, more preferably 95% or more, and still more preferably 99% ormore. The ratio of the 1,4-structural unit may be measured by the samemethod as the method used for measurement of 1,4-structural unit in theabove-mentioned 1,3-cyclohexadiene polymer.

Further, a chain composed of 1,4-structural units of 1,3-cyclohexadiene,which is contained in the CHD-ST copolymer of the present invention, ispreferably high cis-syndiotactic. Specifically, cis-syndiotacticity oftwo successive units of 1,4-structural unit of 1,3-cyclohexadiene isgenerally 50 r % or more, preferably 70 r % or more, and more preferably90 r % or more. The cis-syndiotacticity can be measured by the samemethod as the method used for measurement of cis-syndiotacticity in theabove-mentioned 1,3-cyclohexadiene polymer.

A styrene structural unit contained in the CHD-ST copolymer of thepresent invention is represented by the following formula (A). Here,substituents (R)_(n) on phenyl rings may or may not exist. When thestructural units represented by the formula (A) are arranged in asuccessive manner, the units each generally bind with a head to tailbond. The styrene structural unit contained in the CHD-ST copolymer ofthe present invention may be one kind or two or more kinds.

R and n in the following formula (A) are not particularly limited, butare similar to R and n in the repetitive unit represented by the formula(A) described earlier in the part of the styrene polymer (copolymer),respectively.

In the CHD-ST copolymer of the present invention, a chain composed ofstyrene structural units, which is contained in the copolymer, ispreferably high syndiotactic. Specifically, in the CHD-ST copolymer ofthe present invention, which is a random copolymer, the ratio of diadwhich is a syndiotactic sequence (syndiotacticity) among all twosuccessive units (diad) of styrene structural unit contained in thecopolymer is generally 60 r % or more, preferably 80 r % or more, andmore preferably 98 r % or more. The syndiotacticity of chain composed ofthe styrene structural units can be measured by the same method (byanalysis of ¹³C-NMR spectrum) as the method used for measurement ofsyndiotacticity of a chain composed of styrene structural units in theabove-mentioned ethylene-styrene copolymer.

Mw/Mn as an index of the molecular weight distribution of the CHD-STcopolymer of the present invention is generally 2 or less, andpreferably 1.8 or less. The term “molecular weight distribution” refersto a measurement value (Mw/Mn) obtained by a GPC method (where ameasurement is performed by using polystyrene as a reference materialand tetrahydrofran as an eluate at 40° C.). The molecular weightdistribution may be measured by using a GPC measurement device (TOSOHHLC 8220 GPC/HT), for example.

A molecular weight of the CHD-ST copolymer of the present invention isnot particularly limited, but the number average molecular weight of theCHD-ST copolymer is generally 10,000 or less, and preferably 8,000 orless. A lower limit thereof is not particularly limited, but isparticularly 1,000 or more (preferably 3,000 or more). The molecularweight is related to a content of 1,3-cyclohexadiene structural unit,and there is a tendency that a molecular weight increases as a contentdecreases. The molecular weight can be measured by the same GPC methodused in measurement of the molecular weight distribution.

The CHD-ST copolymer of the present invention generally has a glasstransition temperature. The glass transition temperature is notparticularly limited, but is generally 100° C. or higher (preferably150° C. or higher). The glass transition temperature is measured by adifferential scanning calorimetry (DSC) method.

5. Copolymer of 1,3-cyclohexadiene and ethylene (CHD-ET Copolymer) ofthe Present Invention

The copolymer of 1,3-cyclohexadiene and ethylene (CHD-ET copolymer) ofthe present invention is a polymer including a 1,3-cyclohexadienestructural unit and an ethylene structural unit (preferably consistingof both the units). Here, a content of the 1,3-cyclohexadiene structuralunit in the CHD-ET copolymer of the present invention can be arbitrarilyselected, but is generally 3 to 70 mol %.

The content can be measured by means of ¹H-NMR. For example, as shown inFIG. 12, the content can be determined from the ratio of a peak area ofa peak attributed to olefin hydrogen of the 1,3-cyclohexadienestructural unit at around 5.3 to 5.8 ppm and peak areas of other peaks.

As described later, the content can be controlled by adjusting theamount of 1,3-cyclohexadiene of the monomer to be used as a rawmaterial.

As described above, the CHD-ET copolymer of the present inventionincludes a 1,3-cyclohexadiene structural unit and an ethylene structuralunit, and both the structural units may be arranged in an arbitraryorder. In other words, each of those structural units may be arranged ina random manner, or with a certain regularity (for example, both thestructural units are arranged in an alternate manner, in a successivemanner to some degree, or in other determined order). Therefore, theCHD-ET copolymer of the present invention may be any of a randomcopolymer, an alternate copolymer, a block copolymer, and othersequence-defined copolymer. The CHD-ET copolymer of the presentinvention is preferably a random copolymer or block copolymer, and morepreferably a random copolymer.

A 1,3-cyclohexadiene structural unit contained in the CHD-ET copolymerof the present invention may be a 1,4-structural unit or 1,2-structuralunit. The CHD-ET copolymer of the present invention is characterized byhaving a ratio of 1,4-structural unit {the number of 1,4-structuralunit/(the number of 1,4-structural unit+the number of 1,2-structuralunit)} of generally 80% or more, preferably 90% or more, more preferably95% or more, and still more preferably 99% or more. The ratio can bedetermined form ¹H-NMR spectrum. Specifically, the ratio may be measuredby the same method as the method used for measurement of 1,4-structuralunit in the above-mentioned CHD polymer.

Further, a chain composed of 1,4-structural units of 1,3-cyclohexadienein the CHD-ET copolymer of the present invention is preferably highcis-syndiotactic. Specifically, cis-syndiotacticity of two successiveunits of 1,4-structural unit of 1,3-cyclohexadiene is generally 50 r %or more, preferably 70 r % or more, and more preferably 90 r % or more.The cis-syndiotacticity can be measured by the same method as the methodused for measurement of cis-syndiotacticity in the above-mentioned CHDpolymer.

A molecular weight distribution of the CHD-ET copolymer of the presentinvention is not particularly limited, but Mw/Mn, as an index of themolecular weight distribution, of the CHD-ET copolymer of the presentinvention is generally 1.7 or less, and preferably 1.4 or less. The term“molecular weight distribution” refers to a measurement value (Mw/Mn)obtained by a GPC method (where a measurement is performed by usingpolystyrene as a reference material and 1,2-dichlorobenzene as an eluateat 145° C.). The molecular weight distribution may be measured by usinga GPC measurement device (TOSOH HLC 8121 GPC/HT), for example.

A molecular weight of the CHD-ET copolymer of the present invention isnot particularly limited, but the number average molecular weight of thecopolymer is generally 3×10⁵ or less, and preferably 2×10⁵ or less. Alower limit is not particularly limited, but is preferably 1,000 ormore. The molecular weight is related to a content of structural unitderived from 1,3-cyclohexadiene, and a molecular weight increases as acontent decreases. The molecular weight can be determined by the sameGPC method used for measurement of the molecular weight distribution. Inaddition, by elevating the temperature at a polymerization reaction inproduction of CHD-ET copolymer, the molecular weight can be increased.

The CHD-ET copolymer of the present invention generally has a meltingpoint. The temperature at the melting point is not particularly limited,but is generally about 120 to 130° C. The melting point is measured by adifferential scanning calorimetry (DSC) method.

6. Copolymer of norbornenes/ethylene/styrene (NBE-ET-ST Copolymer) ofthe Present Invention

The term “copolymer of norbornenes/ethylene/styrene of the presentinvention” refers to a polymer including a norbornene structural unit,ethylene structural unit, and styrene structural unit (preferablycomposed of those units). The NBE-ET-ST copolymer of the presentinvention is preferably a terpolymer.

Each of norbornene/ethylene/styrene structural units in the NBE-ET-STcopolymer may be arranged in an arbitrary order. In other words, each ofthose structural units may be arranged in a random manner, or with acertain regularity (for example, each of the structural units isarranged in a successive manner to some degree, or in other determinedorder). Therefore, the NBE-ET-ST copolymer of the present invention maybe any of a random copolymer, an ABC-type block copolymer, and othersequence-defined copolymer. The NBE-ET-ST copolymer of the presentinvention is preferably a random copolymer or ABC-type block copolymer,and more preferably a random copolymer.

The ratios of the respective structural units in the NBE-ET-ST copolymerof the present invention are arbitrary, but the content of ethylenestructural unit with respect to all structural units is generally about20 to 80 mol %. In production of NBE-ET-ST copolymer (described later),the content of the ethylene structural unit can be controlled dependingon the ratio between norbornenes and styrene, pressure of ethylene,amount of solvent, reaction temperature, kind of catalyst (kinds ofcentral metal and ligand), kind of co-catalyst, and the like, and is notlimited to the above-mentioned range.

Further, the ratio between styrene structural unit and norbornenestructural unit in the NBE-ET-ST copolymer of the present invention isarbitrary. The ratio between the units can be controlled by adjustingthe ratio between styrene and norbornenes, which are monomer rawmaterials in production of NBE-ET-ST copolymer (described later).

The content of ethylene structural unit in the NBE-ET-ST copolymer ofthe present invention and the ratio between styrene structural unit andnorbornene structural unit can be measured by analysis of ¹³C-NMRspectrum. Specifically, as shown in FIG. 16, respective peaks of ¹³C-NMRspectrum of the NBE-ET-ST copolymer are attributed to respectivecarbons, so the ratio may be determined on the basis of the peak area.

Specifically, the contents can be determined from the ratio of, forexample, a peak area P₁₂₈ of a peak (ST4 carbon) at around 128 ppm, apeak area P₃₃ of a peak (NBE1 carbon) at around 33 ppm, and a peak areaP_(30.5) of a peak (ET2 carbon+NBE2 carbon) at around 30.5 ppm. That is,the contents can be determined according to the following formulae.Styrene content(%)=(P ₁₂₈/(P ₁₂₈+2×P _(30.5)))×100,Norbornene content(%)=(4×P ₃₃/(P ₁₂₈+2×P _(30.5)))×100,Ethylene content(%)=((2×P _(30.5)−4×P ₃₃)/(P ₁₂₈+2×P _(30.5)))×100

A styrene structural unit contained in the NBE-ET-ST copolymer of thepresent invention is represented by the following formula (A). Here,substituents (R)_(n) on phenyl rings may or may not exist (may beunsubstituted). When the structural units represented by the formula (A)are arranged in a successive manner, the units each generally bind witha head to tail bond. The styrene structural unit contained in theNBE-ET-ST copolymer of the present invention may be one kind or two ormore kinds.

R and n in the following formula (A) are similar to R and n in therepetitive unit represented by the formula (A) described earlier in thepart of the styrene polymer (copolymer), respectively.

Tacticity of the styrene structural unit in the NBE-ET-ST copolymer ofthe present invention is preferably high syndiotactic. Specifically, ofall two successive units (diad) of styrene structural unit contained inthe NBE-ET-ST copolymer of the present invention, which is a randomcopolymer, a ratio of diad which is a syndiotactic sequence is generally60 r % or more, preferably 80 r % or more, and more preferably 98 r % ormore.

The syndiotacticity of chain composed of the styrene structural unitscan be measured by the same method as the method used for measurement ofsyndiotacticity in the above-mentioned styrene-ethylene copolymer.

As described above, the NBE-ET-ST copolymer of the present inventionincludes a norbornene structural unit. Here, the term “norbornenes”refers to compounds each having a 2-norbornene skeleton as shown in thefollowing formula.

In the formula, R¹ and R² are each arbitrary and not particularlylimited, but, for example, they may independently represent a hydrogenatom or an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10carbon atoms), or form an alkylene chain or alkenylene chain incombination with each other. Specific examples of the norbornenesinclude 2-norbornene, dicyclopentadiene, tetracyclododecane (TCD), and1,4-methanotetrahydrofuluorene (MTF).

The norbornenes are preferably 2-norbornene in which R¹ and R² arehydrogen atoms or dicyclopentadiene.

The norbornene structural unit in the NBE-ET-ST copolymer of the presentinvention preferably has high selectivity for addition polymerizationunit. In other words, as a structural unit of polynorbornenes, thefollowing addition polymerization unit and open-ring polymerization unitare possible, and the NBE-ET-ST copolymer of the present invention ischaracterized by having a high ratio of the addition polymerization unitwith respect to all structural units of norbornenes therein.Specifically, the ratio of the addition polymerization unit in allstructural units of norbornenes therein in the NBE-ET-ST copolymer ofthe present invention is generally 95% or more, and preferably near100%. The ratio between the addition polymerization unit and open-ringpolymerization unit can be determined from ¹H-NMR spectrum.

A molecular weight distribution of the NBE-ET-ST copolymer of thepresent invention is not particularly limited, but Mw/Mn as an index ofthe molecular weight distribution of the NBE-ET-ST copolymer of thepresent invention is generally 2.0 or less, and preferably 1.5 or less.The term “molecular weight distribution” refers to a measurement value(Mw/Mn) obtained by a GPC method (where a measurement is performed byusing polystyrene as a reference material and 1,2-dichlorobnezene as aneluate at 145° C.). The molecular weight distribution may be measured byusing a GPC measurement device (TOSOH HLC 8121 GPC/HT), for example.

A molecular weight of the NBE-ET-ST copolymer of the present inventionis not particularly limited, but the number average molecular weight ofthe copolymer is generally 5×10⁵ or less. A lower limit is notparticularly limited, but is preferably 5,000 or more.

The NBE-ET-ST copolymer of the present invention generally has a glasstransition temperature. The glass transition temperature is notparticularly limited, but is generally about 60° C. The glass transitiontemperature is measured by a differential scanning calorimetry (DSC)method.

7. Copolymer of dicyclopentadiene and ethylene (DCPD-ET

copolymer) of the Present Invention

The copolymer of dicyclopentadiene and ethylene of the present inventionis a copolymer including a dicyclopentadiene structural unit and anethylene structural unit. In the DCPD-ET copolymer of the presentinvention, both the structural units may be arranged in an arbitraryorder. In other words, each of those structural units may be arranged ina random manner, or with a certain regularity (for example, both thestructural units are arranged in an alternate manner, in a successivemanner to some degree, or in other determined order). Therefore, theDCPD-ET copolymer of the present invention may be any of a randomcopolymer, an alternate copolymer, a block copolymer, and othersequence-defined copolymer. The DCPD-ET copolymer of the presentinvention is preferably a random copolymer or block copolymer, and morepreferably a random copolymer.

A content of the dicyclopentadiene structural unit with respect to allstructural units contained in the DCPD-ET copolymer of the presentinvention is not particularly limited, but is generally 10 mol % ormore, preferably 20 mol % or more, and more preferably 30 mol % or more.Further, the upper limit of the content is not particularly limited, butis generally 60 mol % or less, preferably 50 mol % or less, and morepreferably 40 mol % or less.

The content can be measured by analysis of ¹H-NMR spectrum.Specifically, as shown in FIG. 19, respective peaks of ¹H-NMR spectrumof the DCPD-ET copolymer are attributed to respective carbons of thecopolymer, so the ratio may be determined on the basis of these peakareas. Specifically, the content can be determined from the ratio of,for example, a peak area P₃ of a peak (DCPD1 hydrogen) at around 3 ppm,and a peak area P_(0.7-1.7) of a peak (DCPD4 hydrogen+ET4 hydrogen) ataround 0.7 to 1.7 ppm. That is, the content can be determined accordingto the following formula.DCPD(%)=(4P ₃/(P _(0.7-1.7)))×100

The content can be controlled by adjusting the using amount (orconcentration) of dicyclopendadiene of a raw material in production of aDCPD-ET copolymer (described later).

Dicyclopentadiene has a C═C double bond derived from a norbornenestructure and a C═C double bond derived from a cyclopentene structure. Aratio of dicyclopentadiene structural unit, which is based on the C═Cdouble bond derived from a norbornene structure, with respect to allstructural units of dicyclopentadiene in the DCPD-ET copolymer of thepresent invention, is generally 80% or more, preferably 90% or more, andmore preferably 99% or more.

In addition, like the norbornene structural unit, a dicyclopentadienestructural unit, which is based on the C═C double bond derived from anorbornene structure, may be an addition polymerization unit oropen-ring polymerization unit as shown in the following formula. Theratio of addition polymerization unit with respect to all structuralunits of dicyclopentadiene in the DCPD-ET copolymer of the presentinvention is generally 80% or more, preferably 90% or more, morepreferably 95% or more, and still more preferably 99% or more.

The content can be determined from ¹H-NMR spectrum data.

A molecular weight distribution of the DCPD-ET copolymer of the presentinvention is not particularly limited, but Mw/Mn as an index of themolecular weight distribution of the DCPD-ET copolymer of the presentinvention is generally 3 or less, and preferably 2 or less. The term“molecular weight distribution” refers to a measurement value (Mw/Mn)obtained by a GPC method (where a measurement is performed by usingpolystyrene as a reference material and 1,2-dichlorobnezene as an eluateat 145° C.). The molecular weight distribution may be measured by usinga GPC measurement device (TOSOH HLC 8121 GPC/HT), for example.

A molecular weight of the DCPD-ET copolymer of the present invention isnot particularly limited, but the number average molecular weight of thecopolymer is generally 100,000 or more, preferably 200,000 or more, morepreferably 300,000 or more, and still more preferably 400,000 or more.An upper limit of the molecular weight is not particularly limited, butthe number average molecular weight of the copolymer only needs to be1,000,000 or less.

The DCPD-ET copolymer of the present invention generally has a glasstransition temperature. The glass transition temperature is notparticularly limited, but generally about 160 to 200° C. The glasstransition temperature is measured by a differential scanningcalorimetry (DSC) method.

(Production Method of Polymer Compound of the Present Invention)

The production method of the polymer compound of the present inventionis characterized by including subjecting an arbitrary polymerizablemonomer to polymerization (or addition polymerization) by using theabove-mentioned polymerization catalyst composition of the presentinvention.

Further, the production method of the present invention may be the sameas the production method of a polymer compound by an additionpolymerization reaction using a conventional coordinated ionicpolymerization catalyst except that the catalyst composition of thepresent invention is used as a polymerization catalyst.

Specifically, the method can be performed by the following procedures.

1. A polymerizable monomer is supplied into a system (preferably aliquid phase) including the catalyst composition of the presentinvention, and is then polymerized. At that time, if the monomer is aliquid, it can be supplied by being dropped, or if the monomer is gas,it may be supplied through a gas pipe (by means of bubbling in the caseof liquid phase reaction system).

2. For the purpose of polymerization, the catalyst composition of thepresent invention is added or each of the components of the catalystcomposition is separately added into a system (preferably a liquidphase) including the polymerizable monomer. The catalyst composition tobe added may be prepared (preferably in a liquid phase), and activatedin advance (in this case, the catalyst composition may be desirablyadded so as not to be touch in the air).

Here, examples of the polymerizable monomer include a monomer capable ofaddition polymerization such as an olefin-based monomer, an epoxy-basedmonomer, an isocyanate-based monomer, a lactone-based monomer, alactide-based polymer, a cyclic carbonate-based monomer, and analkyne-based monomer, and any of them can be used in combination.

Of those, the polymerizable monomer is preferably one kind or two ormore kinds of olefin-based monomers, or more preferably one kind or twoor more kinds of monomers selected from the group consisting of asubstituted or unsubstituted styrene, ethylene, α-olefin (including1-hexene), diene, and cyclic olefin (including norbornenes andcyclohexadiene). Here, examples of the diene as an olefin-based monomerinclude cyclic diene such as 1,3-butadiene, 1,3-pentadiene,1,4-pentadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene,2,4-dimethyl-1,3-pentadiene, 2-methyl-1,3-hexadiene, 2,4-hexadiene, andcyclohexadiene.

The production method may be an arbitrary method such as a gas phasepolymerization method, a solution polymerization method, a suspensionpolymerization method, a liquid phase bulk polymerization method, anemulsion polymerization method, or a solid phase polymerization method.In the case of the solution polymerization method, a solvent to be usedis not particularly limited as long as it is inactive during apolymerization reaction and is a solvent capable of dissolving a monomerand catalyst. Examples of the solvent include: saturated aliphatichydrocarbons such as butane, pentane, hexane, and heptane; saturatedalicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatichydrocarbons such as benzene and toluene; halogenated hydrocarbones suchas methylene chloride, chloroform, carbon teterachloride,trichlorethylene, perchlorethylene, 1,2-dichloroethane, chlorbenzene,brombenzene, and chlortoluene; and ethers such as tetrahydrofran anddiethyl ether.

Further, a solvent with no toxicity to living body is preferable. Aspecific example of the solvent includes aromatic hydrocarbons, withtoluene being particularly preferable. A solvent may be used alone, or amixed solvent of combination of two or more kinds may be used.

An amount of the solvent to be used is arbitrary, but the amount maypreferably allow the concentration of complex contained in thepolymerization catalyst to be 0.1 to 0.0001 mol/l.

A temperature at polymerization when the polymerization of the presentinvention is a solution polymerization may be set in an arbitrary rangeof, for example, −90 to 100° C. The temperature may be arbitrarilyselected depending on the kind of monomer to be polymerized, but isgenerally at around room temperature, that is, about 25° C.

The polymerization time is in a range of about several seconds toseveral hours, and may be arbitrarily selected depending on the kind ofmonomer to be polymerized. In general, the polymerization time may beone hour or less, or one minute or less in some cases.

Of course, those conditions may be arbitrarily selected depending on thetemperature at a polymerization reaction, kind of monomer, molar amount,kind and amount of catalyst composition, and the like, and are notlimited to the above-listed range.

Further, a copolymer can be produced in the following manner.

1) In the case of random copolymer or alternate copolymer, a mixture oftwo or more kinds of monomers can be subjected to a polymerizationreaction under the presence of catalyst composition to produce therandom copolymer or alternate copolymer.

2) In the case of block copolymer, each of monomers can be sequentiallysupplied into a reaction system including a catalyst composition toproduce the block copolymer.

Examples of the polymer compound produced by the production method ofthe present invention include the following, but are not limited tothose compounds.

1) A substituted or unsubstituted styrene polymer, or a copolymer of asubstituted or unsubstituted styrene and a substituted styrene.

2) A copolymer of a substituted or unsubstituted styrene and ethylene.

3) An ethylene polymer.

4) An α-olefin (including 1-hexene) polymer.

5) A copolymer of ethylene and α-olefin (including 1-hexene).

6) A copolymer of ethylene and norbornenes.

7) A 1,3-cyclohexadiene polymer.

8) A copolymer of 1,3-cyclohexadiene and a substituted or unsubstitutedstyrene.

9) A copolymer of 1,3-cyclohexadiene and ethylene.

9) A copolymer of norbornenes, a substituted or unsubstituted styrene,and ethylene.

10) A copolymer of dicyclopentadiene and ethylene.

11) A polymer or a copolymer of diene.

12) A copolymer of a substituted or unsubstituted styrene and aconjugated diene.

Note that production methods of polymers (copolymers) in the items 1)and 2), 7) to 10), and 12) will be described in more detail hereinbelow.

1. Production Method of Styrene Polymer or Copolymer

A styrene polymer or copolymer can be produced by polymerizing asubstituted or unsubstituted styrene, or the mixture thereof(hereinafter, also simply referred to as “styrene compound”) by usingthe catalyst composition of the present invention.

Examples of a complex to be used in the catalyst composition preferablyinclude a complex having a central metal of Scandium (Sc), Yttrium (Y),Gadolinium (Gd), or Lutetium (Lu), or more preferably Scandium (Sc).

On the other hand, as an ionic compound in the catalyst composition, acompound composed of a quadrivalent boron anion and carbonium cationsuch as [Ph₃C][B(C₆F₅)₄] is preferable. The molar ratio between thecomplex and the ionic compound is preferably about 1:1.

Specific procedures includes, for example, composing the catalystcomposition of the present invention in a solvent (preferably toluene)to produce an active species; and supplying a styrene compound in thesolvent while stirring the solvent. The reaction temperature ispreferably set to about 25° C.

An amount of the solvent to be used in a polymerization reaction may bein a ratio of about 5 ml per 1 ml of styrene monomer, but is not limitedto the ratio.

An amount of styrene compound to be provided is preferably 100 to 3,000folds in a molar ratio with respect to a complex, and preferably 500 to2,500 folds when an Sc complex is used. Increase in the ratio makes itpossible to produce a polystyrene polymer (copolymer) having a largermolecular weight, but the ratio largely exceeding 3,000 folds may resultin a slight decrease in syndiotacticity.

In many cases, the polymerization reaction is completed in severalseconds to one hour. In particular, in the case where an Sc complex isused, the reaction is often completed in one minute or less. Aftercompletion of the reaction, the reaction system may have a increasedviscosity and thus can not be stirred in some cases.

After completion of the reaction, a generated polymer can beprecipitated by transferring a reaction mixture into methanol or thelike. A styrene polymer (copolymer) can be obtained by filtrating anddrying the precipitated polymer. An yield of the obtained styrenepolymer (copolymer) can be made almost 100%, though depending on thekind of complex to be used. In particular, use of Sc complex leads to ahigh yield in many cases.

The thus-produced styrene polymer (copolymer) may have highsyndiotacticity. In a particularly preferable embodiment, theabove-mentioned styrene polymer (copolymer) may be produced.

2. Production Method of Ethylene-Styrene Copolymer

An ethylene-styrene copolymer can be produced by polymerizing ethyleneand one or two or more styrene compounds by using the catalystcomposition of the present invention. The kinds of complex and ioniccompound, the relative ratio thereof, and the like in the catalystcomposition are preferably similar to those in the production method inthe above-mentioned styrene polymer or copolymer.

Specific procedures includes, for example, continuously supplyingethylene gas into a solution (preferably a toluene solution) containinga styrene compound, and adding the catalyst compound of the presentinvention into the solution. The reaction temperature is preferably setto about 25° C.

An amount of the solvent to be used in a polymerization reaction ispreferably set to be in a ratio of about 50 ml per 1 ml of styrene, butis not particularly limited to the ratio.

An amount of styrene compound is preferably about 100 to 3,000 folds ina molar ratio with respect to a complex (or an ionic compound). Increasein the amount of a styrene compound may provide an increase in amolecular weight of a copolymer to be obtained, and also an increase ina content of styrene.

A pressure of ethylene gas to be supplied can be arbitrarily adjusted,but only has to be 1 atm in general. Adjustment of the pressure isthought to enable adjustments of a molecular weight of the copolymer anda content of ethylene.

The catalyst composition is preferably added as a solution (preferably asolution containing an active species) which is obtained by a reactionof a complex and an ionic compound in a solvent (preferably toluene) inadvance.

The reaction time is preferably set to several seconds to one hour. Inparticular, in the case where an Sc complex is used, the reaction timeis preferably set to about several minutes.

After completion of the reaction, a generated polymer can beprecipitated by transferring a reaction mixture into methanol or thelike. A ethylene-styrene copolymer can be obtained by filtrating anddrying the precipitated polymer.

The thus-produced ethylene-styrene copolymer is a random copolymer andmay have high syndiotacticity. In a preferable embodiment, theethylene-styrene copolymer may have a sharp molecular weightdistribution.

On the other hand, an ethylene-styrene copolymer, which is a blockcopolymer, can be obtained by: adding the catalyst composition of thepresent invention into a solution (preferably a toluene solution)containing a styrene compound for polymerization; and supplying ethylenegas into the solvent after the styrene compound in the system hasdisappeared (the styrene compound may disappear in several minutes).Note that styrene may be supplied to be polymerized after thepolymerization of ethylene.

The thus-obtained ethylene-styrene copolymer, which is a blockcopolymer, may have a styrene block chain with high syndiotacticity anda sharp molecular weight distribution.

3. Production Method of 1,3-cyclohexadiene Polymer

A 1,3-cyclohexadiene polymer can be produced by polymerizing1,3-cyclohexadiene by using the catalyst composition of the presentinvention. Examples of a complex in the catalyst composition preferablyinclude a complex having a central metal of Scandium (Sc), Yttrium (Y),Lutetium (Lu), Dysprosium (Dy), or Holmium (Ho), Erbium (Er), and morepreferably a complex having a central metal of Scandium (Sc). Thecentral metal is preferably Sc in view of yield of the obtained polymer.On the other hand, examples of an ionic compound of the catalystcomposition of the present invention preferably include a compoundcomposed of a quadrivalent boron anion and carbonium cation such as[Ph₃C][B(C₆F₅)₄], or a compound composed of a quadrivalent boron anionand anilium cation such as [Ph(Me)₂NH][B(C₆F₅)₄]. A molar ratio betweenthe complex and the ionic compound is preferably set to about 1:1.

Specific procedures include, for example, composing the catalystcomposition of the present invention in a solvent (preferably toluene)to produce an active species, and supplying 1,3-cyclohexadiene in theobtained solvent while stirring the solution. The reaction temperatureis preferably set to about 25° C.

An amount of the solvent to be used in a polymerization reaction may bein a ratio of about 5 ml per 10 mmol of 1,3-cyclohexadiene, but is notparticularly limited to the ratio.

An amount of 1,3-cyclohexadiene to be provided is preferably 100 to 3000folds in a molar ratio with respect to a complex. Increase in the ratiomay produce a polystyrene polymer (copolymer) having a larger molecularweight, but the excessively large ratio may lead to a decrease incis-syndiotacticity.

In general, the polymerization reaction is completed in about severalhours.

After completion of the reaction, a generated polymer can beprecipitated by transferring a reaction mixture into methanol or thelike. A 1,3-cyclohexadiene polymer can be obtained by filtrating anddrying the precipitated polymer. An yield of the obtained1,3-cyclohexadiene polymer can be made near 50%, though depending on thekind of complex to be used.

The thus-produced 1,3-cyclohexadiene polymer has high 1,4-selectivityand may have high cis-syndiotacticity. In a particularly preferableembodiment, the above-mentioned 1,3-cyclohexadiene polymer may beproduced.

4. Production Method of Copolymer of 1,3-cyclohexadiene and Styrene

A copolymer of 1,3-cyclohexadiene and styrene can be produced bypolymerizing 1,3-cyclohexadiene and a substituted or unsubstitutedstyrene by using the catalyst composition of the present invention. Thekinds of complex and ionic compound, the relative ratio thereof, and thelike in the catalyst composition are preferably similar to those in theproduction method in the above-mentioned 1,3-cyclohexadiene polymer.

Specific procedures include, for example, composing the catalystcomposition of the present invention in a solvent (preferably toluene)to produce an active species, and supplying 1,3-cyclohexadiene andstyrene in the solvent while stirring the solvent. 1,3-cyclohexadieneand styrene each may be provided in a state of being dissolved in asolvent (for example, toluene). A random copolymer can be obtained bysupplying a mixture of 1,3-cyclohexadiene and styrene, and polymerizingthem. A block copolymer can be obtained by: supplying one of1,3-cyclohexadiene and styrene; polymerizing the one; and supplying theother one for polymerization (living copolymerization).

The reaction temperature is preferably set to about 25° C.

An amount of the solvent to be used in a polymerization reaction ispreferably in a ratio of about 5 to 10 ml per total 20 mmol of1,3-cyclohexadiene and styrene, but is not particularly limited to theratio.

Amounts of 1,3-cyclohexadiene and styrene to be provided is eachpreferably 100 to 3,000 folds, and more preferably 100 to 1,000 folds ina molar ratio with respect to a complex. Increase in the ratio makes itpossible to produce a polymer having a larger molecular weight, but theexcessively large ratio may lead to a decrease in tacticity of each of1,3-cyclohexadiene structural unit and styrene structural unit.

In general, the polymerization reaction is completed in about severalhours.

After completion of the reaction, a generated polymer can beprecipitated by transferring a reaction mixture into methanol or thelike. A 1,3-cyclohexadiene-styrene copolymer can be obtained byfiltrating and drying the precipitated polymer.

The thus-produced 1,3-cyclohexadiene and styrene copolymer has a highratio of 1,4-structural unit with respect to all structural units in1,3-cyclohexadiene, and may have high cis-syndiotacticity. Further, the1,3-cyclohexadiene and styrene copolymer may have a styrene structuralunit with high syndiotacticity. In a preferable embodiment, theabove-mentioned CHD-ST copolymer of the present invention may beproduced.

5. Production Method of Copolymer of 1,3-cyclohexadiene and Ethylene

A copolymer of 1,3-cyclohexadiene and ethylene can be produced bypolymerizing 1,3-cyclohexadiene and ethylene by using the catalystcomposition of the present invention. The kinds of complex and ioniccompound, the relative ratio thereof, and the like in the catalystcomposition are preferably similar to those in the production method ofthe above-mentioned 1,3-cyclohexadiene polymer.

Specific procedures for obtaining a random copolymer include, forexample, continuously supplying ethylene gas into a solution (preferablya toluene solution) containing 1,3-cyclohexadiene, and adding thecatalyst composition of the present invention into the solution.

A block copolymer can be obtained, for example, by: adding the catalystcomposition of the present invention into a solution containing1,3-cyclohexadiene to polymerize the 1,3-cyclohexadiene; and supplyingethylene gas into the solvent for polymerization.

An amount of the solvent to be used in a polymerization reaction may bein a ratio of about 20 to 40 ml per 1.0 g of 1,3-cyclohexadiene, but isnot particularly limited to the ratio.

An amount of 1,3-cyclohexadiene may be about 100 to 3,000 folds in amolar ratio with respect to a complex (or an ionic compound). There is atendency that an increase in the amount of 1,3-cyclohexadiene results ina decrease in a molecular weight and an increase in a content of1,3-cyclohexadiene.

The reaction temperature may be set to about 25° C. By increasing thereaction temperature, a molecular weight of the obtained copolymer maybe increased.

A pressure of ethylene gas to be supplied can be arbitrarily adjusted,but only has to be 1 atm in general. Adjustment of the pressure isthought to enable adjustments of a molecular weight of a copolymer and acontent of ethylene.

The catalyst composition is preferably added as a solution (preferably asolution containing an active species) which is obtained by a reactionof a complex and an ionic compound in a solvent (preferably toluene) inadvance.

In general, the polymerization reaction is completed in about severalhours.

After completion of the reaction, a generated copolymer can beprecipitated by transferring a reaction mixture into methanol or thelike. A 1,3-cyclohexadiene-ethylene copolymer can be obtained byfiltrating and drying the precipitated polymer. In a particularlypreferable embodiment, the above-mentioned CHD-ET copolymer of thepresent invention may be produced.

6. Production Method of Copolymer of Ethylene, Substituted orUnsubstituted Styrene, and Norbornenes

A copolymer of ethylene, substituted or unsubstituted styrene, andnorbornenes can be produced by copolymerization of ethylene, substitutedor unsubstituted styrene, and norbornenes by using the catalystcomposition of the present invention. The kinds of complex and ioniccompound, the relative ratio thereof, and the like in the catalystcomposition are preferably similar to those in the production method inthe above-mentioned 1,3-cyclohexadiene polymer.

Here, the term “norbornenes” has the same meaning as that of thenorbornenes described in the above-mentioned NBE-ET-ST copolymer of thepresent invention.

Specific procedures for obtaining a random copolymer include, forexample, continuously supplying ethylene gas into a solution (preferablya toluene solution) containing norbornenes and a substituted orunsubstituted styrene, and adding the catalyst composition of thepresent invention into the solution.

An ABC-type block copolymer can be obtained, for example, by: adding thecatalyst composition of the present invention into a solution containingone of norbornenes and styrene; polymerizing the one; adding the otherone to be polymerized; and supplying ethylene gas.

An amount of the solvent to be used in a polymerization reaction may bein a ratio of about 40 ml per 20.0 mmol of norbornenes, but is notparticularly limited to the ratio.

An amount of norbornenes to be used may be about 100 to 3,000 folds in amolar ratio with respect to a complex (or an ionic compound), but is notparticularly limited to the ratio.

An amount of styrene to be used may be adjusted depending on a contentof styrene structural unit in the copolymer of interest (in the case ofhigh content of styrene structural unit in the copolymer of interest,the amount of styrene may be increased).

A pressure of ethylene gas to be supplied can be arbitrarily adjusted,but only has to be 1 atm in general. Adjustment of the pressure isthought to enable adjustments of a molecular weight of copolymer and acontent of ethylene.

The reaction temperature is preferably set to about 25° C. By increasingthe reaction temperature, a molecular weight of the obtained copolymermay be increased.

The catalyst composition is preferably added as a solution (preferably asolution containing an active species) which is obtained by a reactionof a complex and an ionic compound in a solvent (preferably toluene) inadvance.

In general, the polymerization reaction is completed in about severalminutes.

After completion of the reaction, a generated copolymer can beprecipitated by adding methanol into a reaction mixture. A copolymer ofethylene, a substituted or unsubstituted styrene, and norbornenes can beobtained by filtrating and drying the precipitated polymer. In aparticularly preferable embodiment, the above-mentioned NBE-ET-STcopolymer of the present invention may be produced.

7. Production Method of Copolymer of Dicyclopentadiene and Ethylene

A copolymer of dicyclopentadiene and ethylene can be produced bycopolymerization of dicyclopentadiene and ethylene by using the catalystcomposition of the present invention. The kinds of complex and ioniccompound, the relative ratio thereof, and the like in the catalystcomposition are preferably similar to those in the production method inthe above-mentioned 1,3-cyclohexadiene polymer.

Specific procedures for obtaining a random copolymer include, forexample, continuously supplying ethylene gas into a solution (preferablya toluene solution) containing dicyclopentadiene, and adding thecatalyst composition of the present invention into the solution.

A block copolymer can be obtained by: adding the catalyst composition ofthe present invention into a solution containing dicyclopentadiene;polymerizing the dicyclopentadiene; and supplying ethylene gas forpolymerization (block copolymerization).

An amount of the solvent to be used in a polymerization reaction may bein a ratio of about 40 ml per 20.0 mmol of dicyclopentadiene, but is notparticularly limited to the ratio.

An amount of dicyclopentadiene to be used may be about 100 to 3,000folds in a molar ratio with respect to a complex (or an ionic compound).Further, it goes without saying that an increase in an amount ofdicyclopentadiene results in a high content of dicyclopentadienestructural unit in the obtained copolymer.

A pressure of ethylene gas to be supplied can be arbitrarily adjusted,but only has to be 1 atm in general. Adjustment of the pressure isthought to enable adjustments of a molecular weight of a copolymer andan content of ethylene.

The catalyst composition is preferably added as a solution (preferably asolution containing an active species) which is obtained by a reactionof a complex and an ionic compound in a solvent (preferably toluene) inadvance.

In general, the polymerization reaction is completed in about severalminutes.

After completion of the reaction, a generated copolymer can beprecipitated by adding methanol or the like into a reaction mixture. Acopolymer of dicyclopentadiene and ethylene can be obtained byfiltrating and drying the precipitated polymer. In a particularlypreferable embodiment, the above-mentioned DCPD-ET copolymer of thepresent invention may be produced.

8. Production Method of Conjugated Diene-Styrene Copolymer

A conjugated diene-styrene copolymer can be produced by polymerizationof one or two or more conjugated diene and one or two or more styrenecompounds by using the catalyst composition of the present invention.The kinds of complex and ionic compound, the relative ratio thereof, andthe like in the catalyst composition are preferably similar to those inthe production method of the above-mentioned styrene polymer orcopolymer.

Examples of specific procedures will be shown below, but the proceduresare not particularly limited to those examples.

A solution containing the catalyst composition of the present inventionis prepared. An example of the solvent of the solution includes toluene.A mixture, which is obtained by adding a styrene compound and conjugateddiene, is stirred in the prepared solution to undergo a polymerizationreaction. An amount of the solvent to be used in a polymerizationreaction is preferably in a ratio of about 1 to 10 ml per 1 ml ofmonomer mixture. An amount of styrene compound may be about 100 to 2,000folds in a molar ratio with respect to a complex (or an ionic compound).

A ratio between the styrene compound and conjugated diene(styrene/conjugated diene) is arbitrary, but may be set to 0.5 to 8 in amolar ratio. By adjusting the ratio between the styrene compound andconjugated diene, a content ratio between a styrene structural unit andconjugated diene structural unit in the obtained copolymer can beadjusted.

The reaction temperature is preferably set to about 25° C. The reactiontime varies depending on a volume ratio between a styrene compound andconjugated diene compound or the like, which are to be polymerized, butis preferably about 1 to 5 hours. Extension of the reaction time mayresult in a high ratio of a styrene content of the obtained copolymer.

After completion of the reaction, a generated polymer can beprecipitated by: stopping the polymerization reaction by addition ofmethanol to a reaction mixture; and transferring the reaction mixtureinto methanol. A conjugated diene-styrene copolymer can be obtained byfiltrating and drying the precipitated polymer.

EXAMPLES

Hereinafter, the present invention will be described in more detail withreference to examples and reference examples. However, the scope of thepresent invention is not limited by those examples. Note that themeasurement of ¹³C-NMR was performed at frequency of 75.5 MHz.

Reference Example

(Synthesis of Metallocene Complex)

Synthesis was performed according to the method described in thefollowing literatures (1) and (2).

(1) Tardif, O.; Nishiura, M.; Hou, Z. M. Organometallics 22, 1171,(2003).

(2) Hultzsch, K. C.; Spaniol, T. P.; Okuda, J. Angew. Chem. Int. Ed, 38,227, (1999).

1. Synthesis of (C₅Me₄SiMe₃)Sc(CH₂SiMe₃)₂(THF)

ScCl₃ and LiCH₂SiMe₃ were reacted with each other in a ratio of 1:3 inTHF, and a solution (10 ml) of Sc(CH₂SiMe₃)₃ (1.366 g, 3.03 mmol) inhexane was prepared from the reaction product. C₅Me₄H(SiMe₃) (0.589 g,3.03 mmol) was added to the prepared solution at room temperature. Theobtained pale yellow solution was stirred at room temperature for twohours.

After the stirring, the resultant solution was concentrated underreduced pressure, and the obtained residual oil was cooled at −30° C.overnight, to thereby obtain (C₅Me₄SiMe₃)Sc(CH₂SiMe₃)₂(THF) (1.145 g,2.36 mmol, 78% yield) as a colorless cubic crystal.

Physical property data of (C₅Me₄SiMe₃)Sc(CH₂SiMe₃)₂(THF) will be shownbelow.

¹H-NMR (C₆D₆, 22° C.): δ (ppm) −0.30 (d, 2H, CH₂SiMe₃, J_(H-H)=11.5 Hz),−0.25 (d, 2H, CH₂SiMe₃, J_(H-H)=11.5 Hz) 0.29 (s, 18H, CH₂SiMe₃), 0.43(s, 9H, C₅Me₄SiMe₃), 1.19 (m, 4H, THF-b-CH₂), 1.91 (s, 6H, C₅Me₄), 2.22(s, 6H, C₅Me₄), 3.63 (m, 4H, THF-a-CH₂).

¹³C-NMR (C₆D₆, 22° C.): δ (ppm) 2.83 (s, 3C, C₅Me₄SiMe₃), 4.62 (s, 6C,CH₂SiMe₃), 12.12 (s, 2C, C₅Me₄), 15.43 (s, 2C, C₅Me₄), 24.93 (s, 2C,THF), 40.41 (s, 1C, CH₂SiMe₃), 71.51 (s, 2C, THF), 116.64 (s, 1C,ipso-C₅ (SiMe₃)Me₄, 124.15 (s, 2C, C₅Me₄), 127.96 (s, 2C, C₅Me₄).

IR (nujol): 628 (s), 672 (s), 713 (s), 755 (s), 819 (s), 851 (s), 889(s), 1013 (s), 1038 (m), 1131 (m), 1175 (w), 1238 (s), 1247 (s), 1280(w), 1328 (s), 1344 (m), 1407 (w).

Anal. Calcd for C₂₄H₅₁OScSi₃: C, 59.45; H, 10.60. Found: C, 58.54; H,10.41.

2. Synthesis of (C₅Me₄SiMe₃)Ln(CH₂SiMe₃)₂(THF) (Ln=Y, Gd, Ho, and Lu)

Synthesis was performed in the same manner as that in theabove-mentioned (C₅Me₄SiMe₃)Sc(CH₂SiMe₃)₂(THF).

3. Synthesis of (C₅Me₅)Sc(CH₂C₆H₄NMe₂-o)₂

To a solution (10 ml) of Sc(CH₂C₆H₄NMe₂-o)₃ (1.323 g, 3 mmol) in THF,pentamethylcyclopentadiene (409 mg, 3 mmol) was added. The solution wasstirred at 70° C. for 12 hours and then concentrated under reducedpressure to obtain a yellow powder. The obtained yellow powder waswashed with hexane, and recrystallized from benzene, to thereby obtain(C₅Me₅)Sc(CH₂C₆H₄NMe₂-o)₂ (538 mg, 40% yield) as a yellow crystal.

Physical property data of (C₅Me₅)Sc(CH₂C₆H₄NMe₂-o)₂ will be shown below.

¹H-NMR (C₆D₆, 60° C.): δ (ppm) 7.13 (d, J=7.3 Hz, 2H, aryl), 6.99 (t,J=7.4 Hz, 2H, aryl), 6.71 to 6.83 (m, 4H, aryl), 2.35 (s, 12H, NMe₂),1.73 (s, 15H, C₅Me₅), 1.47 (s, 4H, CH₂)

¹³C-NMR (C₆D₆, 60° C.): δ (ppm) 11.8 (CpMe), 45.5 (br NMe₂), 47.3 (CH₂),117.1, 119.6, 120.9, 126.5, 130.7, 145.7, 147.7 (aromatic and Cp ringcarbons).

Anal. Calcd for C₂₈H₃₉ScN₂: C, 74.97; H, 8.76; N, 6.24. Found: C, 74.89;H, 8.67; N, 6.19.

Example 1 Production of Styrene Polymer

To a 100 ml-glass reaction vessel, a solution (5 ml) of(C₅Me₄SiMe₃)Sc(CH₂SiMe₃)₂(THF) (10 mg, 21 μmol) in toluene and asolution (7 ml) of [Ph₃C][B(C₆F₅)₄](19 mg, 21 μmol) in toluene weresuccessively added. After one minute, styrene (2.148 g, 21 mmol) wasadded to the obtained solution while the solution was vigorously stirred(stirred by a magnetic stirrer). Viscosity of the solution increased inseveral seconds to stop the stirring. The reaction mixture was pouredinto methanol (400 ml) to precipitate a polymer. The polymer of a whitepowder was filtrated, and dried at 60° C. under reduced pressure, tothereby obtain 2.14 g (constant weight) (100%) of polymer.

Examples 2 to 9 Production of Styrene Polymer

(1) Example 2: polystyrene was obtained by the same method as that ofExample 1 except that the amount of styrene was changed to 10.5 mmol.

(2) Example 3: polystyrene was obtained by the same method as that ofExample 1 except that the amount of styrene was changed to 14.7 mmol.

(3) Example 4: polystyrene was obtained by the same method as that ofExample 1 except that the amount of styrene was changed to 31.5 mmol.

(4) Example 5: polystyrene was obtained by the same method as that ofExample 1 except that the amount of styrene was changed to 42.0 mmol.

(5) Example 6: polystyrene was obtained by the same method as that ofExample 1 except that the amount of styrene was changed to 52.5 mmol.

(6) Example 7: polystyrene was obtained by the same method as that ofExample 1 except that: the complex was changed to(C₅Me₄SiMe₃)Y(CH₂SiMe₃)₂(THF) (21 μmol); the amount of styrene waschanged to 2.1 mmol; and the reaction time was changed to 30 minutes.

(7) Example 8: polystyrene was obtained by the same method as that ofExample 7 except that the complex was changed to(C₅Me₄SiMe₃)Gd(CH₂SiMe₃)₂(THF) (21 μmol).

(8) Example 9: polystyrene was obtained by the same method as that ofExample 7 except that the complex was changed to(C₅Me₄SiMe₃)Lu(CH₂SiMe₃)₂(THF) (21 μmol).

(9) Example 10: to a 100 ml-flask, a solution (50 ml) of(C₅Me₅)Sc(CH₂C₆H₄NMe₂-o)₂ (11 mg, 0.025 mmol) in toluene and a solution(7 ml) of [Ph₃C][B(C₆F₅)₄] (23 mg, 0.025 mmol) in toluene weresuccessively added. After 10 minutes, styrene (10.415 g, 100 mmol) wasadded to the obtained solution while the solution was vigorouslystirred. Viscosity of the reaction solution increased in several minutesto stop the stirring.

The reaction mixture was poured into methanol (400 ml) to precipitate apolymer of a white powder. The filtrated precipitate was dried at 60° C.under reduced pressure to obtain a polymer (10.42 g, 100%).

(10) Comparative Example 1: An experiment was performed by the samemethod as that of Example 1 except that the complex was changed to(C₅Me₄SiMe₂CH₂PPh₂)Y(CH₂SiMe₃)₂(THF) (21 μmol), but polystyrene was notobtained.

Table 1 provides a summary of the production methods of Examples 1 to 10and the physical properties of the styrene polymers obtained by themethods.

TABLE 1 Number Styrene/ average Complex molecular Molecular MeltingExample Central (molar Reaction Yield Syndiotactic weight weight pointNo metal ratio) time (%) Activity polystyrene (×10⁻⁴) distribution (°C.) 2 Sc 500 <1 min 100 ≧3125 100% 8.85 1.38 271 3 Sc 700 <1 min 100≧4376 100% 11.96 1.29 271 1 Sc 1000 <1 min 100 ≧6034 100% 13.55 1.45 2724 Sc 1500 <1 min 100 ≧9362 100% 18.96 1.55 271 5 Sc 2000 <1 min 100≧12498 100% 26.94 1.36 272 6 Sc 2500 <1 min 87.2 13618 100% 37.86 1.37272 7 Y 100 30 min 60.3 13 100% 1.07 1.39 269 8 Gd 100 30 min 69.1 15100% 0.92 1.35 269 9 Lu 100 30 min 25.2 6 100% 0.49 1.38 268 10 Sc 400010 min 100 2510 100% 115 1.54 271

In Table 1:

1. the yield was calculated from (mass of obtained styrenepolymer)/(mass of used styrene monomer);

2. the activity is represented by weight of polymer in kg, which isproduced by a reaction for 1 hour using 1 mol of complex;

3. the content of syndiotactic polystyrene was calculated from (mass ofinsoluble polymer in 2-butanone being refluxed)/(mass of all obtainedpolymer); and

syndiotacticity of each of the polystyrene was 99% or more in terms of apentad indication (rrrr) from NMR spectrum data (an NMR measurementsolvent was 1,2-dichlorobenzene-d₄, and the measurement temperature wasset to 130° C.);

4. the number average molecular weight and the molecular weightdistribution were each determined by a GPC method (the measurement wasat 145° C. performed by using polystyrene as a reference material and1,2-dichlorobenzen as an eluate); and

5. the melting point was measured by a DSC method.

As shown in Table 1, syndiotacticity of each of the polystyrene polymersobtained in Examples 1 to 10 was 100%. Further, from the fact that eachof Mw/Mn, which is an index of a molecular weight distribution of theobtained styrene polymer, was 1.55 or less, the distribution was foundto be narrow.

Further, it was found that adjustment of a ratio between styrene monomerand complex allows adjustment of the molecular weight.

As described above, syndiotacticity (pentad) of the styrene polymer ofthe present invention can be determined from ¹³C-NMR spectrum.Specifically, the syndiotacticity can be determined from an integrationratio of a peak to be attributed to aromatic C1 carbon, or a peak to beattributed to polystyrene main chain carbon.

For example, FIG. 1 shows a ¹³C-NMR spectrum chart of the styrenepolymer obtained in Example 1, and from the figure, it is found that apeak of c (at about 145 ppm) to be attributed to aromatic C1 carbon ofracemic pentad is extremely sharp and has syndiotacticity of almost 100rrrr %. Further, it is found that peaks of a and b each of which is tobe attributed to polystyrene main chain carbon of racemic pentad arealso extremely sharp and have syndiotacticity of almost 100 rrrr %.

Example 11 Production of Ethylene-Styrene Copolymer or the Like

In a glove box, to a two-necked, 250 ml-glass-made reaction vesselprovided with a stirrer bar, toluene (35 ml) and styrene (2.148 g, 21mmol) were added. The glass-made reaction vessel was taken out of theglove box and connected to a Schlenk line. The temperature of thereaction vessel was kept to 25° C. by using a water bath.

Ethylene gas (1 atm) was continuously supplied into the reaction vesselwhile a mixture in the reaction vessel was rapidly stirred.

On the other hand, (C₅Me₄SiMe₃)Sc(CH₂SiMe₃)₂(THF) (10 mg, 21 μmol) and[Ph₃C][B(C₆F₅)₄] (19 mg, 21 μmol) were reacted with each other in atoluene solution (15 ml) to generate a predetermined amount of activespecies in the system. The obtained solution was rapidly added to thereaction vessel by syringe to initiate polymerization.

After two minutes, methanol was added to the reaction vessel toterminate the polymerization reaction, and the reaction mixture waspoured into methanol (400 ml) to precipitate a polymer. The precipitatedpolymer was filtrated, and dried at 60° C. under reduced pressure, tothereby obtain 0.79 g (constant weight) of polymer.

Examples 12 to 16 Production of Ethylene-Styrene Copolymer (RandomCopolymer) or the Like

(1) Example 12: an ethylene-styrene copolymer was obtained by the samemethod as that of Example 11 except that the amount of styrene waschanged to 10 mmol.

(2) Example 13: an ethylene-styrene copolymer was obtained by the samemethod as that of Example 11 except that the amount of styrene waschanged to 31 mmol.

(3) Example 14: an ethylene-styrene copolymer was obtained by the samemethod as that of Example 11 except that the amount of styrene waschanged to 41 mmol.

(4) Example 15: a styrene copolymer was obtained by the same method asthat of Example 11 except that supply of ethylene was stopped.

(5) Example 16: an ethylene copolymer was obtained by the same method asthat of Example 11 except that the amount of styrene was changed to 0mmol.

Table 2 provides a summary of the production methods of polymers ofExamples 11 to 16 and the physical properties of the polymers obtainedby the methods.

TABLE 2 Number average Molecular Content of molecular weight MeltingExample Styrene Ethylene Yield styrene Syndiotacticity weightdistribution point No (mmol) (atm) (g) Activity (mol %) (r %) (×10⁻⁴)(Mw/Mn) (° C.) 16 0 1 0.55 786 0 17.23 1.72 127 15 21 0 0.45 643 1006.04 1.41 268 12 10 1 0.40 600 9 >98 7.92 1.14 — 11 21 1 0.79 112356 >98 11.13 1.19 214 13 31 1 0.92 1314 68 >98 16.26 1.17 233 14 41 11.62 2314 91 >98 15.09 1.26 245

In Table 2:

1. the activity is represented by weight of polymer in kg, the polymerbeing produced by reaction for 1 hour using 1 mol of complex;

2. the content of polystyrene was determined from ¹³C-NMR spectrum data(an NMR measurement solvent was 1,2-dichlorobenzene-d₄, and themeasurement temperature was set to 130° C.);

3. the number average molecular weight and the molecular weightdistribution (Mw/Mn) were each determined by a GPC method (themeasurement was performed at 145° C. by using polystyrene as a referencematerial and 1,2-dichlorobenzen as an eluate); and

4. the melting point was measured by a DSC method.

As described above, syndiotacticity (diad r %) of the ethylene-styrenecopolymer of the present invention can be determined from ¹³C-NMRspectrum.

FIGS. 2 and 3 show ¹³C-NMR spectrum chars of ethylene-styrene copolymersof Examples 11 to 14, and an enlarged part (about 24 to 48 ppm) of FIG.2, respectively.

All peaks observed in a range of about 145.6 to 146.2 ppm are attributedto racemic diad (r), so it is found that the copolymer hassyndiotacticity of almost 100%.

Example 17 Production of Ethylene-Styrene Copolymer (Block Copolymer) orthe Like

In a glove box, to a 100 ml-two-necked flask provided with a stirrerbar, toluene (35 ml) and styrene (2.148 g, 21 mmol) were added and theresultant solution was stirred. The flask was taken out of the glove boxand connected to a Schlenk line. The temperature of the flask was keptto 25° C. by using a water bath and argon gas was supplied thereto.

On the other hand, (C₅Me₄SiMe₃)Sc(CH₂SiMe₃)₂ (THF) (10 mg, 21 μmol) and[Ph₃C][B(C₆F₅)₄](19 mg, 21 μmol) were reacted with each other in atoluene solution (15 ml) to generate a predetermined amount of activespecies in the system. The obtained solution was rapidly added to thereaction vessel by syringe to initiate polymerization.

Two minutes after the initiation of polymerization, ethylene gas (1 atm)was supplied to the reaction vessel for 1 minute.

After that, methanol (2 ml) was added to terminate the polymerizationreaction, and the reaction mixture was poured into methanol (400 ml) toprecipitate a polymer. The precipitated polymer was filtrated, and driedat 60° C. under reduced pressure, to thereby obtain 1.092 g (constantweight) of a white polymer. Physical properties of the obtained polymerare shown below.

Number average molecular weight: 1.12×10⁵

Molecular weight distribution (Mw/Mn): 1.23

Content of styrene: 82%

Note that, in Example 17, when the reaction was stopped before supply ofethylene gas (in other words, ethylene gas was not supplied), 0.5 g(constant weight) of polymer (styrene sole polymer) was obtained.Physical properties of the polymer are shown below.

Number average molecular weight: 0.60×10⁵

Molecular weight distribution (Mw/Mn): 1.23

Example 18 Production of Isoprene-Styrene Copolymer

To a 100 ml-flask in a glove box, (C₅Me₄SiMe₃) Sc(CH₂SiMe₃)₂ (THF) (10mg, 21 μmol) and [Ph₃C][B(C6F₅)₄](19 mg, 21 μmol) were added, andtoluene (30 ml) was further added. To the obtained solution a mixture ofstyrene (2.148 g, 21 mmol) and isoprene (1.431 g, 21 mmol) was added,and the whole was subjected to a polymerization reaction at 25° C. After12 hours, methanol was added to stop the polymerization reaction. Thereaction mixture was poured into methanol (200 ml) to precipitate apolymer. The precipitated polymer was filtrated, and dried at 60° C.under reduced pressure, to thereby obtain 1.64 g of isoprene-styrenecopolymer.

Examples 19 to 21 Production of Isoprene-Styrene Copolymer

An isoprene-styrene copolymer was obtained in a similar manner as thatin Example 18 except that the amounts of styrene and isoprene werechanged as shown in the following table.

TABLE 3 Number average Molecular Reaction Content of molecular weightStyrene Isoprene time Yield styrene weight distribution SyndiotacticityExample (mmol) (mmol) (h) (g) (%) (×10⁻³) (Mw/Mn) (r %) 18 21 21 12 1.6425 3.91 1.84 100 19 21 7.34 2 0.36 50 3.92 1.16 100 20 37 7.34 2 0.74 706.14 1.29 100 21 52 7.34 2 0.98 86 8.62 1.28 100 Syndiotacticityrepresents a ratio of diad which is a syndiotactic sequence to all twosuccessive units (diad) of styrene unit.

Example 22 Production of Ethylene Polymer

In a glove box, (C₅Me₄SiMe₃)Sc(CH₂SiMe₃)₂ (THF) (10 mg, 21 μmol),[Ph₃C][B(C₆F₅)₄](19 mg, 21 μmol), and toluene (50 ml) were added to a250 ml-two-necked flask at room temperature. The flask was taken out ofthe glove box and connected to a Schlenk line. The temperature of theflask was kept to 25° C. by using a water bath.

Ethylene gas (1 atm) was continuously supplied into the flask while amixture in the flask was rapidly stirred to cause bubbling and to allowthe polymerization reaction to proceed for 10 minutes. After completionof the reaction, the reaction mixture was poured into methanol (400 ml)to precipitate a polymer. The polymer of a white powder was filtrated,and dried at 60° C. under reduced pressure, to thereby obtain 4.39 g(constant weight) of polymer. FIG. 4 shows a ¹³C-NMR spectrum chart ofthe polymer (a measurement solvent was 1,2-dichlorobenzene-d₄, and themeasurement temperature was set to 130° C.).

Examples 23 to 30 Production of ethylene polymer

(1) Example 23: an ethylene polymer was obtained by the same method asthat of Example 22 except that the complex was changed to(C₅Me₄SiMe₃)Gd(CH₂SiMe₃)₂ (THF)

(2) Example 24: an ethylene polymer was obtained by the same method asthat of Example 22 except that the complex was changed to(C₅Me₄SiMe₃)Y(CH₂SiMe₃)₂ (THF)

(3) Example 25: an ethylene polymer was obtained by the same method asthat of Example 22 except that the complex was changed to(C5Me₄SiMe₃)Ho(CH₂SiMe₃)₂ (THF).

(4) Example 26: an ethylene polymer was obtained by the same method asthat of Example 22 except that the complex was changed to(C₅Me₄SiMe₃)Lu(CH₂SiMe₃)₂ (TF).

(5) Example 27: an ethylene polymer was obtained by the same method asthat of Example 22 except that the complex was changed to (C5Me₄SiMe₃)Er(CH₂SiMe₃)₂ (THF).

(6) Example 28: an ethylene polymer was obtained by the same method asthat of Example 22 except that the complex was changed to (C₅Me₄SiMe₃)Dy (CH₂SiMe₃)₂ (THF)

(7) Example 29: an ethylene polymer was obtained by the same method asthat of Example 22 except that the complex was changed to (C₅Me₄SiMe₃)Tb (CH₂SiMe₃)₂ (THF).

(8) Example 30: an ethylene polymer was obtained by the same method asthat of Example 22 except that the complex was changed to (C₅Me₄SiMe₃)Tm (CH₂SiMe₃)₂ (THF)

Table 4 provides a summary of the production methods of Examples 22 to30 and the physical properties of the styrene polymers obtained by themethods.

TABLE 4 Concen- Number Ex- tration average Molecular am of Activitymolecular weight ple Central complex × Yield (kg/mol · weightdistribution No metal 10⁴ mol/L (g) h · atm) ×10⁻⁵ (Mw/Mn) 22 Sc 6.6004.39 798 2.19 2.14 23 Gd 5.024 1.65 591 1.84 1.96 24 Y 6.429 4.22 7883.11 1.79 25 Ho 6.613 3.95 716 2.01 1.98 26 Lu 6.506 0.612 226 0.96 3.4027 Er 6.588 3.98 726 2.92 1.84 28 Dy 6.640 3.03 553 2.65 1.85 29 Tb6.680 2.65 476 2.61 1.96 30 Tm 6.570 2.26 413 2.32 2.23

In Table 4:

1. the activity is represented by weight of polymer in kg, which isproduced by a reaction for 1 hour using 1 mol of complex; and

2. the number average molecular weight and the molecular weightdistribution (Mw/Mn) were each determined by a GPC method (themeasurement was performed at 145° C. by using polystyrene as a referencematerial and 1,2-dichlorobenzen as an eluate).

As shown in Table 4, the composition of the present invention containingas a central metal a group III metal or a lanthanoid metal can be usedas a polymerization catalyst composition.

Example 31 Production of 1-hexene polymer

In a glove box, a solution (5 ml) of (C₅Me₄SiMe₃) Sc(CH₂SiMe₃)₂ (THF)(10 mg, 21 μmol) in toluene and a solution (8 ml) of [Ph₃C][B(C₆F₅)₄](19 mg, 21 μmol) in toluene were added to a 100 ml-glass-made reactionvessel at room temperature.

After several minutes, 1-hexene (1.736 g, 21 mmol) was added to theobtained wine red catalyst solution while the solution was stirred. Thepolymerization reaction was allowed to proceed for minutes. Aftercompletion of the reaction, methanol (70 ml) was added thereto toprecipitate an oil-state polymer. The obtained polymer was dried at 60°C. under reduced pressure, to thereby obtain 1.684 g (constant weight)(97%) of polymer. FIG. 4 shows a ¹³C-NMR spectrum chart of the polymer(a measurement solvent was 1,2-dichlorobenzene-d₄, and the measurementtemperature was set to 130° C.).

Examples 32 to 35 Production of 1-hexene Polymer

(1) Example 32: a 1-hexene polymer was obtained by the same method asthat of Example 31 except that: the reaction temperature was changed to−30° C.; and the reaction time was changed to 60 minutes.

(2) Example 33: a 1-hexene polymer was obtained by the same method asthat of Example 31 except that: the amount of 1-hexane was changed to2.604 g; and the reaction time was changed to 30 minutes.

(3) Example 34: a 1-hexene polymer was obtained by the same method asthat of Example 31 except that the complex was changed to(C₅Me₅)Sc(CH₂SiMe₃)₂ (THF) (21 μmol).

(4) Example 35: a 1-hexene polymer was obtained by the same method asthat of Example 31 except that the complex was changed to (C₅(SiMe₃)₂H₃)Sc (CH₂SiMe₃)₂ (THF) (21 μmol).

TABLE 5 Number average Ligand of Reaction molecular Molecular Examplecomplex Molar ratio of Reaction time Yield weight weight No Cp*hexene/complex solvent (minute) (%) ×10⁻³ distribution 31 C₅Me₄SiMe₃1000 Toluene 15 97 5.76 1.65 32 C₅Me₄SiMe₃ 1000 Toluene 60 73 347.2 1.4633 C₅Me₄SiMe₃ 1500 Toluene 30 90 5.74 1.67 34 C₅Me₅ 1000 Toluene 15 645.60 1.58 35 C₅(SiMe₃)₂H₃ 1000 Toluene 15 26 4.84 1.51

In Table 5:

1. the yield was calculated from (mass of polymer obtained)/(mass ofmonomer used); and

2. the number average molecular weight and the molecular weightdistribution (Mw/Mn) were each calculated by a GPC method (themeasurement was performed at 40° C. by using polystyrene as a referencematerial and THF as an eluate).

Example 36 Production of 1-hexene-ethylene Copolymer

In a glove box, 1-hexene (1.736 g, 21 mmol) and toluene (15 ml) wereadded to a 250-ml glass-made two-necked flask provided with a stirrerbar. The reaction vessel was taken from the glove box and connected to aSchlenk line. The temperature of the flask was kept to 25° C. by using awater bath, and ethylene gas (1 atm) was supplied thereto to causebubbling while the content therein was rapidly stirred.

In toluene (15 ml), (C₅Me₄SiMe₃)Sc(CH₂SiMe₃)₂ (THF) (10 mg, 21 μmol) and[Ph₃C][B(C₆ F₅)₄](19 mg, 21 μmol) were reacted to each other to generatea predetermined amount of active species in the system. The obtainedsolution was rapidly added to the above-mentioned solution ofhexene-ethylene in toluene by using a syringe to initiate apolymerization reaction. After 5 minutes, methanol was added thereto toterminate the polymerization reaction. The reaction mixture was pouredinto methanol (400 ml) to precipitate a polymer. The precipitatedpolymer was filtrated, and dried at 60° C. under reduced pressure, tothereby obtain 1.92 g (constant weight) of polymer. FIG. 4 shows a¹³C-NMR spectrum chart of the polymer (the measurement was performed at120° C. by using 1,1,2,2-tetrachloroethane-d₂ as a measurement solvent).

Examples 37 to 49 Production of 1-hexene-ethylene Copolymer

(1) Example 37: a polymer was obtained by the same method as that inExample 36 except that the amount of 1-hexene was changed to 10 mmol.

(2) Example 38: a polymer was obtained by the same method as that inExample 36 except that the amount of 1-hexene was changed to 31 mmol.

(3) Example 39: a polymer was obtained by the same method as that inExample 36 except that the amount of 1-hexene was changed to 41 mmol.

(4) Example 40: a polymer was obtained by the same method as that inExample 36 except that the amount of 1-hexene was changed to 62 mmol.

(5) Example 41: a polymer was obtained by the same method as that inExample 36 except that the reaction time was changed to 3 minutes.

(6) Example 42: a polymer was obtained by the same method as that inExample 36 except that the reaction time was changed to 7 minutes.

(8) Example 43: a polymer was obtained by the same method as that inExample 36 except that the reaction time was changed to minutes.

(9) Example 44: a polymer was obtained by the same method as that inExample 36 except that the reaction time was changed to minutes.

(10) Example 45: a polymer was obtained by the same method as that inExample 36 except that the complex was changed to (C₅Me₅)Sc(CH₂SiMe₃)₂(THF)

(11) Example 46: a polymer was obtained by the same method as that inExample 45 except that: the amount of 1-hexene was changed to 31 mmol;and the reaction time was changed to 3 minutes.

(12) Example 47: a polymer was obtained by the same method as that inExample 45 except that: the amount of 1-hexene was changed to 41 mmol;and the reaction time was changed to 3 minutes.

(13) Example 48: a polymer was obtained by the same method as that inExample 45 except that the amount of 1-hexene was changed to 31 mmol.

(14) Example 49: a polymer was obtained by the same method as that inExample 45 except that and the reaction time was changed to 15 minutes.

FIG. 6 provides a summary of the production methods of Examples 36 to 49and the physical properties of the copolymers obtained by the methods.

TABLE 6 Content Ligand of Reaction of polymerization Number averageMolecular Example complex 1-hexene time Activity 1-hexene rate of1-hexene molecular weight weight No Cp* (mmol) (minute) Yield (g)(kg/(mol Sc · h)) (mol %) (%) ×10⁻⁴ distribution 37 C₅Me₄SiMe₃ 10 5 1.69965 4 22 6.17 3.40 36 C₅Me₄SiMe₃ 21 5 1.92 1098 11 29 2.77 2.74 38C₅Me₄SiMe₃ 31 5 2.71 1547 12 30 2.04 2.99 39 C₅Me₄SiMe₃ 41 5 3.17 181013 37 2.26 2.09 40 C₅Me₄SiMe₃ 62 5 3.75 2145 27 38 1.21 2.37 41C₅Me₄SiMe₃ 21 3 1.76 1676 6 15 1.67 3.30 42 C₅Me₄SiMe₃ 21 7 3.48 1420 840 2.33 3.52 43 C₅Me₄SiMe₃ 21 10 4.84 1383 6 42 5.43 4.38 44 C₅Me₄SiMe₃21 15 5.55 1057 12 91 6.00 3.12 45 C₅Me₅ 21 5 0.99 565 27 3 18.39 1.9246 C₅Me₅ 31 3 1.10 1047 12 12 1.95 2.37 47 C₅Me₅ 41 3 1.32 1257 10 93.78 1.87 48 C₅Me₅ 31 5 2.64 1510 8 21 4.07 2.12 49 C₅Me₅ 21 15 2.61 4985 19 14.21 2.40

In Table 6:

1. the content of 1-hexene was calculated from ¹H-NMR spectrum(measurement was performed at 120° C. by using 1 μl,2,2-tetrachloroethane-d₂ as a measurement solvent); and

2. the number average molecular weight and the molecular weightdistribution (Mw/Mn) were each measured by a GPC method (polystyrene and1,2-dichlorobenzene were used as a reference material and an eluate,respectively).

Example 50 Production of Copolymer of styrene and p-methylstyrene

In a glove box, (C₅Me₄SiMe₃)Sc(CH₂SiMe₃)₂ (THF) (10 mg, 21 μmol) and[Ph₃C][B(C₆F₅)₄](19 mg, 21 μmol) were added to toluene (30 ml) in a 100ml-reaction vessel. Further, a mixture of styrene (4.076 g, 39 mmol) and4-methylstyrene (0.243 g, 2 mmol) was added thereto to allow apolymerization reaction at 25° C. After 5 minutes, methanol was addedthereto to terminate the polymerization reaction. The reaction mixturewas poured into methanol (200 ml) to precipitate a polymer. Theprecipitated polymer was filtrated, and dried at 60° C. under reducedpressure, to thereby obtain 4.32 g (constant weight) of polymer.

Examples 51 to 58 Production of Copolymer of styrene and p-methylstyrene

(1) Example 51: a polymer was obtained by the same method as that inExample 50 except that the molar ratio between styrene and4-methylstyrene was changed to 90:10 (total molar amount was 41 mmol).

(2) Example 52: a polymer was obtained by the same method as in Example50 except that the molar ratio between styrene and 4-methylstyrene waschanged to 70:30 (total molar amount was 41 mmol).

(3) Example 53: a polymer was obtained by the same method as in Example50 except that the molar ratio between styrene and 4-methylstyrene waschanged to 50:50 (total molar amount was 41 mmol).

(4) Example 54: a polymer was obtained by the same method as in Example50 except that the molar ratio between styrene and 4-methylstyrene waschanged to 30:70 (total molar amount was 41 mmol).

(5) Example 55: a polymer was obtained by the same method as in Example50 except that the molar ratio between styrene and 4-methylstyrene waschanged to 5:95 (total molar amount was 41 mmol).

(6) Example 56: a polymer was obtained by the same method as in Example50 except that: 4-methylstyrene was changed to 4-t-butylstyrene; and themolar ratio between styrene and 4-t-butylstyrene was changed to 50:50(total molar amount was 41 mmol).

(7) Example 57: a polymer was obtained by the same method as in Example56 except that the molar ratio between styrene and 4-t-butylstyrene waschanged to 70:30 (total molar amount was 41 mmol).

(8) Example 58: a polymer was obtained by the same method as in Example56 except that the molar ratio between styrene and 4-t-butylstyrene waschanged to 30:70 (total molar amount was 41 mmol).

Table 7 provides a summary of the production methods of Examples 50 to58 and the physical properties of the copolymers obtained by themethods.

TABLE 7 Number Molar ratio of average styrene/ Content of molecularMolecular Example Substituted substituted Syndiotacticity styrene weightweight No styrene styrene Yield % (rrrr %) (mol %) ×10⁻⁴ distribution 50p-Me Styrene 95/5  100 >98 95 31.49 1.33 51 p-Me Styrene 90/10 100 >9890 33.75 1.42 52 p-Me Styrene 70/30 100 >98 70 28.99 1.39 53 p-MeStyrene 50/50 100 >98 50 29.69 1.35 54 p-Me Styrene 30/70 100 >98 3030.84 1.36 55 p-Me Styrene  5/95 97 >98 5 28.71 1.56 56 p-Bu^(t) Styrene50/50 99 >98 50 25.54 1.49 57 p-Bu^(t) Styrene 70/30 99 >98 70 29.371.65 58 p-Bu^(t) Styrene 30/70 100 >98 30 29.41 1.38

In Table 7:

1. the yield was calculated from (mass of polymer obtained/mass ofmonomer used);

2. the content of styrene was calculated from ¹³C-NMR spectrum and¹H-NMR spectrum (measurement was performed at 130° C. by using1,2-dichlorobenzene as a measurement solvent);

3. the number average molecular weight and the molecular weightdistribution (Mw/Mn) were each measured by a GPC method (the measurementwas performed by using polystyrene as a reference material and1,2-dichlorobenzene as an eluate); and

4. the syndiotacticity was determined from ¹³C-NMR spectrum.

Example 59 Production of Copolymer of ethylene and norbornene

In a glove box, to a two-necked flask provided with a dropping funnel,which contains 2 ml of a solution (21 ml) of (C₅Me₄SiMe₃) Sc (CH₂SiMe₃)₂(THF) (10 mg, 21 μmol) in toluene and toluene (8 ml), a solution (15 ml)of norbornene (1.88 g, 20.0 mmol) in toluene, 2 ml of a solution (21 ml)of [Ph₃C][B(C₆F₅)₄](19 mg, 21 μmol) in toluene, and toluene (13 ml) wereadded (total volume of toluene was 40 ml).

The flask was taken out of the glove box, set in a water bath (25° C.),and connected to each of a Schlenk line, ethylene gas supply line, and amercury-sealed stopper. The solution in the dropping funnel was droppedto the flask with supply of ethylene gas. After dropping, apolymerization reaction was allowed to proceed for 5 minutes and thenmethanol (25 ml) was added thereto to terminate the polymerizationreaction.

The precipitated polymer was filtrated and washed with methanol. Theresultant polymer was dried at 60° C. under reduced pressure for 24hours. The obtained crude product was extracted by toluene at roomtemperature, to thereby obtain 0.67 g of ethylene-norbornene alternatecopolymer.

Examples 60 to 74 Production of Copolymer of ethylene and norbornene

(1) Example 60: a polymer was obtained by the same method as that inExample 59 except that the complex was changed to{1,3-(SiMe₃)₂C₅H₃}Sc(CH₂SiMe₃)₂ (THF).

(2) Example 61: a polymer was obtained by the same method as that inExample 59 except that the reaction temperature was changed to 0° C.

(3) Example 62: a polymer was obtained by the same method as that inExample 59 except that the reaction temperature was changed to 50° C.

(4) Example 63: a polymer was obtained by the same method as that inExample 59 except that the reaction temperature was changed to 70° C.

(5) Example 64: a polymer was obtained by the same method as that inExample 59 except that the total volume of toluene was adjusted to 60ml.

(6) Example 65: a polymer was obtained by the same method as that inExample 59 except that the total volume of toluene was adjusted to 20ml.

(7) Example 66: a polymer was obtained by the same method as that inExample 59 except that the total volume of toluene was adjusted to 10ml.

(8) Example 67: a polymer was obtained by the same method as that inExample 59 except that the amount of norbornene was changed to 2.82 g.FIG. 5 shows a ¹³C-NMR spectrum chart of the polymer (the measurementwas performed at 130° C. by using 1,2-dichlorobenzene-d₄ as ameasurement solvent).

(9) Example 68: a polymer was obtained by the same method as that inExample 59 except that the amount of norbornene was changed to 3.76 g.

(10) Example 69: a polymer was obtained by the same method as that inExample 59 except that the reaction time was changed to 1 minute.

(11) Example 70: a polymer was obtained by the same method as that inExample 59 except that the reaction time was changed to 3 minutes.

(12) Example 71: a polymer was obtained by the same method as that inExample 59 except that the reaction time was changed to 15 minutes.

(13) Example 72: a polymer was obtained by the same method as that inExample 59 except that the reaction time was changed to 30 minutes.

(14) Example 73: a polymer was obtained by the same method as that inExample 59 except that the amount of [Ph₃C][B(C₆F₅)₄] to be used waschanged to 0.

(15) Example 74: a polymer was obtained by the same method as that inExample 59 except that the amount of (C₅Me₄SiMe₃)Sc(CH₂SiMe₃)₂ (THF) tobe used was changed to 0.

Table 8 provides a summary of the production methods of Examples 59 to74 and the physical properties and the like of the polymers obtained bythe methods. NB represents a norbornene. The numeral “1” in the columnof catalyst composition represents (C₅Me₄SiMe₃)Sc(CH₂SiMe₃)₂ (THF), andthe numeral “2” represents {1,3-(SiMe₃)₂C₅H₃}Sc(CH₂SiMe₃)₂ (THF).

TABLE 8 Number average Reaction Reaction Reaction Content molecularMolecular Melting Example Catalyst temperature volume NB time Yield ofNB weight weight point No composition (° C.) (mL) (g) (min) (g) Activity(mol %) (×10⁻⁴) distribution (° C.) 73 1 25 40 1.88 5 trace — — — — — 74borate 25 40 1.88 5 — — — — — — 59 1/borate 25 40 1.88 5 0.67 8 41.2 111.79 126 60 2/borate 25 40 1.88 5 0.47 5.6 36.1 4.9 1.89 105 61 1/borate0 40 1.88 5 0.35 4.2 35.7 12.1 1.49 104 62 1/borate 50 40 1.88 5 0.819.7 42.5 8 1.81 119 63 1/borate 70 40 1.88 5 0.97 11.6 43.2 4 2.33 12764 1/borate 25 60 1.88 5 0.62 7.4 35.8 15.4 1.65 105 65 1/borate 25 201.88 5 1.29 15.5 46.4 6.5 1.92 134 66 1/borate 25 10 1.88 5 0.37 4.448.1 3.2 2.08 128 67 1/borate 25 40 2.82 5 2.1 25.2 44.2 8.5 2.19 108 681/borate 25 40 3.76 5 0.31 3.7 45.5 7.4 1.8 120 69 1/borate 25 40 1.88 10.4 24 45.2 7 1.62 130 70 1/borate 25 40 1.88 3 0.57 11.4 44.8 8.2 1.74129 71 1/borate 25 40 1.88 15 0.99 4 37.7 5.5 2.41 118 72 1/borate 25 401.88 30 1.2 2.4 36.4 4.6 2.62 109

In Table 8:

1. the activity is represented by weight of polymer in kg, which isproduced by a reaction for 1 hour using 1 mol of complex;

2. the number average molecular weight and the molecular weightdistribution (Mw/Mn) were each measured by a GPC method (polystyrene wasused as a reference material); and

3. the melting point was measured by a DSC method.

Note that all the polymers obtained in Examples 59 to 72 wereethylene-norbornene alternate copolymers.

Example 75 Stereospecific Polymerization Reaction of 1,3-cyclohexadiene

In a glove box, a solution (3 ml) of [Ph₃C][B(C₆F₅)₄](37 mg, 40 μmol) intoluene was added to a solution (2 ml) of (C₅Me₄SiMe₃) Sc (CH₂SiMe₃)₂(THF) (19 mg, 40 μmol) in toluene in a 100-ml flask. The obtainedmixture was stirred at room temperature for several minutes, and then1,3-cyclohexadiene (0.8 g, 10 mmol) was added to the mixture while thesolution was vigorously stirred. After 3 hours, the flask was taken outof the glove box, and methanol was added to the flask to stop thepolymerization. The obtained reaction mixture was poured into methanol(200 ml), and the precipitated white polymer powder was filtrated. Thefiltrated powder was dried at 60° C. under reduced pressure, to therebyobtain 0.44 g (55%) of polymer product. The obtained product wasdissolved in dichlorobenzene at 120° C.

Examples 76 to 82 Stereospecific Polymerization Reaction of1,3-cyclohexadiene

(1) Example 76: 0.16 g (24%) of polymer product was obtained by the samemethod as that in Example 75 except that [Ph (Me)₂ NH][B (C₆F₅)₄](32 mg,40 μmol) was used instead of [Ph₃C][B(C₆F₅)₄](37 mg, 40 μmol). Theobtained product was dissolved in dichlorobenzene at 120° C.

(2) Example 77: 0.34 g (43%) of polymer product was obtained by the samemethod as that in Example 75 except that (C₅Me₅) Sc(CH₂SiMe₃)₂ (THF) (17mg, 40 μmol) was used instead of (C₅Me₄SiMe₃)Sc(CH₂SiMe₃)₂ (THF) (19 mg,40 μmol). The obtained product was dissolved in dichlorobenzene at 120°C.

(3) Example 78: 0.30 g (38%) of polymer product was obtained by the samemethod as that in Example 75 except that (C₅Me₄SiMe₃)Y(CH₂SiMe₃)₂ (THF)(21 mg, 40 μmol) was used instead of (C₅Me₄SiMe₃)Sc(CH₂SiMe₃)₂ (THF) (19mg, 40 μmol). The obtained product was dissolved in dichlorobenzene at120° C.

(4) Example 79: 0.29 g (36%) of polymer product was obtained by the samemethod as that in Example 75 except that (C₅Me₄SiMe₃)Lu(CH₂SiMe₃)₂ (THF)(25 mg, 40 μmol) was used instead of (C₅Me₄SiMe₃)Sc(CH₂SiMe₃)₂ (THF) (19mg, 40 μmol). The obtained product was dissolved in dichlorobenzene at120° C.

(5) Example 80: 0.39 g (49%) of polymer product was obtained by the samemethod as that in Example 75 except that (C₅Me₄SiMe₃)Dy(CH₂SiMe₃)₂ (THF)(24 mg, 40 μmol) was used instead of (C₅Me₄SiMe₃)Sc(CH₂SiMe₃)₂ (THF) (19mg, 40 μmol). The obtained product was dissolved in dichlorobenzene at120° C.

(6) Example 81: 0.40 g (50%) of polymer product was obtained by the samemethod as that in Example 75 except that (C₅Me₄SiMe₃)Ho(CH₂SiMe₃)₂ (THF)(19 mg, 40 μmol) was used instead of (C₅Me₄SiMe₃)Sc(CH₂SiMe₃)₂ (THF) (19mg, 40 μmol). The obtained product was dissolved in dichlorobenzene at120° C.

(7) Example 82: 0.37 g (46%) of polymer product was obtained by the samemethod as that in Example 75 except that (C₅Me₄SiMe₃)Er(CH₂SiMe₃)₂ (THF)(24 mg, 40 μmol) was used instead of (C₅Me₄SiMe₃)Sc(CH₂SiMe₃)₂ (THF) (19mg, 40 μmol). The obtained product was dissolved in dichlorobenzene at120° C.

Table 9 provides a summary of the physical properties and the like ofthe polymer products obtained in Examples 75 to 82.

TABLE 9 Number Molecular average weight molecular distri- Melting Ratioof Cis-syndio- weight bution point 1,4-unit tacticity Example75 15002.46 230° C. >99% 77rrrr % Example76 4400 2.37 250° C. >99% 83rrrr %Example77 3500 2.02 221° C. >99% 99rrrr % Example78 3700 2.12 230°C. >99% 75rrrr % Example79 2900 2.18 224° C. >99% 71rrrr % Example802900 2.55 230° C. >99% 72rrrr % Example81 3400 2.16 231° C. >99% 73rrrr% Example82 6200 2.38 227° C. >99% 70rrrr %

Example 83 Copolymerization Reaction of 1,3-cyclohexadiene and styrene

In a glove box, a solution (3 ml) of [Ph₃C][B(C₆F₅)₄](61 mg, 67 μmol) intoluene was added to a solution (2 ml) of (C₅Me₄SiMe₃)Sc(CH₂SiMe₃)₂(THF) (32 mg, 67 μmol) in toluene in a 100-ml flask. The obtainedmixture was stirred at room temperature for several minutes, and then asolution (5 ml) of 1,3-cyclohexadiene (1.26 g, 15.75 mmol) and styrene(0.55 g, 5.25 mmol) in toluene was added to the mixture while themixture was vigorously stirred. After 3 hours, the flask was taken outof the glove box, and methanol was added to the flask to stop thepolymerization. The obtained reaction mixture was poured into methanol(200 ml), and the precipitated white polymer powder was filtrated. Thefiltrated powder was dried at 60° C. under reduced pressure, to therebyobtain 0.99 g (activity: 4.9 kg copolymer/mol Sc h) of polymer product.The obtained product was dissolved in THF.

Examples 84 to 88 Copolymerization Reaction of 1,3-cyclohexadiene andstyrene

(1) Example 84: 1.13 g (activity: 5.6 kg copolymer/mol Sc h) of polymerproduct was obtained by the same method as that in Example 83 exceptthat: the amount of 1,3-cyclohexadiene was changed from 1.26 g (15.75nmol) to 1.12 g (14.00 mmol); and the amount of styrene was changed from0.55 g (5.25 mmol) to 0.72 g (7.00 mmol). The obtained product wasdissolved in THF.

(2) Example 85: 1.33 g (activity: 6.6 kg copolymer/mol Sc h) of polymerproduct was obtained by the same method as that in Example 83 exceptthat: the amount of 1,3-cyclohexadiene was changed from 1.26 g (15.75mmol) to 0.96 g (12.00 mmol); and the amount of styrene was changed from0.55 g (5.25 mmol) to 0.94 g (9.00 mmol). The obtained product wasdissolved in THF.

(3) Example 86: 1.46 g (activity: 7.3 kg copolymer/mol Sc h) of polymerproduct was obtained by the same method as that in Example 83 exceptthat: the amount of 1,3-cyclohexadiene was changed from 1.26 g (15.75mmol) to 0.84 g (10.50 mmol); and the amount of styrene was changed from0.55 g (5.25 mmol) to 1.09 g (10.50 mmol). The obtained product wasdissolved in THF.

(4) Example 87: 1.60 g (activity: 8.0 kg copolymer/mol Sc h) of polymerproduct was obtained by the same method as that in Example 83 exceptthat: the amount of 1,3-cyclohexadiene was changed from 1.26 g (15.75mmol) to 0.56 g (7.00 mmol); and the amount of styrene was changed from0.55 g (5.25 mmol) to 1.46 g (14.00 mmol). The obtained product wasdissolved in THF.

(5) Example 88: 2.00 g (activity: 10.0 kg copolymer/mol Sc h) of polymerproduct was obtained by the same method as that in Example 83 exceptthat: the amount of 1,3-cyclohexadiene was changed from 1.26 g (15.75mmol) to 0.42 g (5.25 mmol); and the amount of styrene was changed from0.55 g (5.25 mmol) to 1.64 g (15.75 mmol)

The obtained product was dissolved in THF.

Table 10 shows physical properties of the polymer products obtained inExamples 83 to 88.

TABLE 10 Number average Molecular Glass Ratio of molecular weighttransition Content of 1,4-unit of Syndiotacticity of weight distributiontemperature cyclohexadiene cyclohexadiene styrene structural unitExample 83 3100 1.75 173° C. 73 mol % >99% — Example 84 3200 1.76 179°C. 65 mol % >99% — Example 85 3500 1.79 190° C. 45 mol % >99% — Example86 3900 1.76 205° C. 39 mol % >99%   50r % Example 87 4200 1.93 236° C.22 mol % >99% >80r % Example 88 8500 1.90 100° C. 16 mol % >99% >85r %(Melting point 183° C.)

Example 89 Copolymerization Reaction of 1,3-cyclohexadiene and ethylene

In a glove box, a solution (15 ml) of 1,3-cyclohexadiene (0.4 g, 5.0mmol) in toluene was charged into a two-necked flask provided with astirrer bar. The flask was taken out of the glove box, set in a waterbath (25° C.), and connected to each of a Schlenk ethylene line and amercury-sealed stopper by using a three-way cock. Ethylene gas (1 atm)was supplied into the system, and the solution was stirred for 1 minuteto be saturated with the ethylene gas.

On the other hand, a catalyst toluene solution (5 ml) was obtained from(C₅Me₄SiMe₃)Sc(CH₂SiMe₃)₂ (THF) (19 mg, 40 μmol) and [Ph₃C][B(C₆F₅)₄](37mg, 40 μmol). The catalyst toluene solution was added to the solution of1,3-cyclohexadiene by using a syringe while the solution was vigorouslystirred.

After 5 minutes, methanol (200 ml) was added thereto to stop thepolymerization reaction. The precipitated polymer product was filtrated.The filtrated product was washed with methanol and dried at 60° C., tothereby obtain 1.31 g (activity: 3.9×105 g copolymer/mol Sc h atm) ofpolymer product. The obtained product was dissolved in dichlorobenzeneat 145° C.

Examples 90 to 96 Copolymerization Reaction of 1,3-Cyclohexadiene andEthylene

(1) Example 90: 0.87 g of polymer product was obtained by the samemethod as that in Example 89 except that the amount of1,3-cyclohexadiene was changed from 0.4 g (5.0 mmol) to 0.5 g (6.3mmol). The obtained product was dissolved in dichlorobenzene at 145° C.

(2) Example 91: 0.35 g of polymer product was obtained by the samemethod as that in Example 89 except that the amount of1,3-cyclohexadiene was changed from 0.4 g (5.0 mmol) to 0.6 g (7.5mmol). The obtained product was dissolved in dichlorobenzene at 145° C.

(3) Example 92: 0.29 g of polymer product was obtained by the samemethod as that in Example 89 except that the amount of1,3-cyclohexadiene was changed from 0.4 g (5.0 mmol) to 0.8 g (10.0mmol). The obtained product was dissolved in dichlorobenzene at 145° C.

(4) Example 93: 2.00 g of polymer product was obtained by the samemethod as that in Example 89 except that the temperature of water bathwas changed from 25° C. to 50° C. The obtained product was dissolved indichlorobenzene at 145° C.

(5) Example 94: 0.15 g of polymer product was obtained by the samemethod as that in Example 89 except that the amount of1,3-cyclohexadiene was changed from 0.4 g (5.0 mmol) to 1.0 g (12.5mmol). The obtained product was dissolved in dichlorobenzene at 145° C.

(6) Example 95: 0.08 g of polymer product was obtained by the samemethod as that in Example 89 except that the amount of1,3-cyclohexadiene was changed from 0.4 g (5.0 mmol) to 1.2 g (15.0mmol). The obtained product was dissolved in dichlorobenzene at 145° C.

(7) Example 96: 0.20 g of polymer product was obtained by the samemethod as that in Example 89 except that: the amount of1,3-cyclohexadiene was changed from 0.4 g (5.0 mmol) to 2.0 g (25.0mmol); and the temperature of the water bath was changed from 25° C. to50° C. The obtained product was dissolved in dichlorobenzene at 145° C.

Table 11 shows physical properties of the polymer compositions obtainedin Examples 89 to 96.

TABLE 11 Number Molecular Ratio of average weight Content 1,4-unitmolecular distri- Melting of cyclo- of cyclo- weight bution pointhexadiene hexadiene Example89 105800 1.54 126° C. 10 mol % >99%Example90 49800 1.66 124° C. 22 mol % >99% Example91 33900 1.43 126° C.39 mol % >99% Example92 27700 1.36 126° C. 44 mol % >99% Example93115500 1.69 126° C. 22 mol % >99% Example94 27100 1.31 124° C. 46 mol% >99% Example95 2500 1.67 126° C. 51 mol % >99% Example96 3000 1.65123° C. 67 mol % >99%

Example 97 Terpolymerization Reaction of ethylene/styrene/norbornene

In a glove box, a solution (35 ml) of 2-norbornene (1.88 g, mmol) andstyrene (0.52 g, 5 mmol) in toluene was charged into a two-necked flaskprovided with a stirrer bar. The flask was taken out of the glove box,set in a water bath (25° C.), and connected to each of a Schlenkethylene line and a mercury-sealed stopper by using a three-way cock.Ethylene gas (1 atm) was supplied into the system, and the solution wasstirred for 1 minute to be saturated with the ethylene gas.

On the other hand, a catalyst toluene solution (5 ml) was obtained from(C₅Me₄SiMe₃)Sc(CH₂SiMe₃)₂ (THF) (10 mg, 21 μmol) and [Ph₃C][B(C₆F₅)₄](19mg, 21 μmol). The obtained catalyst toluene solution was added to thesolution of norbornene-styrene by using a syringe while the solution wasvigorously stirred. Viscosity of the reaction mixture of the solutionrapidly increased.

After 5 minutes, methanol (200 ml) was added thereto to stop thepolymerization reaction. The precipitated polymer product was filtrated,washed with methanol, and dried at 60° C., to thereby obtain 2.93 g(activity: 1.7×10⁶ g terpolymer/mol Sc h atm) of polymer product. Theobtained product was dissolved in dichlorobenzene at 145° C.

Examples 98 to 101 Terpolymerization Reaction ofethylene/styrene/norbornene

(1) Example 98: 2.69 g of polymer product (activity: 1.5×10⁶ gterpolymer/mol Sc h atm) was obtained by the same method as that inExample 97 except that the amount of styrene was changed from 0.52 g (5mmol) to 1.04 g (10 mmol). The obtained product was dissolved indichlorobenzene at 145° C.

(2) Example 99: 3.00 g of polymer product (activity: 1.7×10⁶ gterpolymer/mol Sc h atm) was obtained by the same method as that inExample 97 except that the amount of styrene was changed from 0.52 g (5mmol) to 2.08 g (20 mmol). The obtained product was dissolved indichlorobenzene at 145° C.

(3) Example 100: 3.45 g of polymer product (activity: 2.0×10⁶ gterpolymer/mol Sc h atm) was obtained by the same method as that inExample 97 except that the amount of styrene was changed from 0.52 g (5mmol) to 3.12 g (30 mmol). The obtained product was dissolved indichlorobenzene at 145° C.

(4) Example 101: 1.16 g of polymer product (activity: 0.7×10⁶ gterpolymer/mol Sc h atm) was obtained by the same method as that inExample 97 except that the amount of styrene was changed from 0.52 g (5mmol) to 4.16 g (40 mmol). The obtained product was dissolved indichlorobenzene at 145° C.

Table 12 shows physical properties of the polymer compositions obtainedin Examples 97 to 101.

TABLE 12 Number Molecular Glass average weight transi- Content Contentmolecular distri- tion tem- of sty- of nor- weight bution perature renebornene Example97 288000 1.47 63° C.  7 mol % 39 mol % Example98 3220001.56 62° C. 10 mol % 35 mol % Example99 379000 1.56 62° C. 15 mol % 32mol % Example100 458000 1.57 62° C. 30 mol % 30 mol % Example101 4880001.59 61° C. 38 mol % 25 mol %

Example 102 Copolymerization Reaction of dicyclopentadiene and ethylene

In a glove box, a solution (35 ml) of dicyclopentadiene (2.64 g, 20mmol) in toluene was charged into a two-necked flask. The flask wastaken out of the glove box, set in a water bath (25° C.), and connectedto each of a Schlenk ethylene line and a mercury-sealed stopper by usinga three-way cock. Ethylene gas (1 atm) was supplied into the system, andthe solution was stirred for 1 minute to be saturated with the ethylenegas.

On the other hand, a catalyst toluene solution (5 ml) was prepared from(C₅Me₄SiMe₃)Sc(CH₂SiMe₃)₂ (THF) (10 mg, 21 μmol) and [Ph₃C][B(C₆F₅)₄](19 mg, 21 μmol). The prepared catalyst solution was added to thesolution of dicyclopentadiene and ethylene by using a syringe while thesolution was vigorously stirred. Viscosity of the reaction mixturerapidly increased.

After 5 minutes, methanol (200 ml) was added thereto to stop thepolymerization reaction. The precipitated polymer product was filtrated,washed with methanol, and dried at 60° C., to thereby obtain 2.3 g(1.3×10⁶ g copolymer/mol Sc h atm) of polymer product. The obtainedproduct was dissolved in dichlorobenzene at 145° C.

Examples 103 and 104 Copolymerization Reaction of dicyclopentadiene andethylene

(1) Example 103: 3.2 g of polymer product (1.8×10⁶ g copolymer/mol Sc hatm) was obtained by the same method as that in Example 102 except thatthe amount of dicyclopentadiene was changed from 2.64 g (20 mmol) to3.96 g (30 mmol). The obtained product was dissolved in dichlorobenzeneat 145° C.

(2) Example 104: 4.0 g of polymer product (2.3×10⁶ g copolymer/mol Sc hatm) was obtained by the same method as that in Example 102 except thatthe amount of dicyclopentadiene was changed from 2.64 g (20 mmol) to5.28 g (40 mmol). The obtained product was dissolved in dichlorobenzeneat 145° C.

Table 13 shows physical properties of the polymer products obtained inExamples 102 to 104.

TABLE 13 Number Molecular Glass average weight transi- Content moleculardistri- tion tem- of dicyclo- weight bution perature pentadieneExample102 494000 2.8 171° C. 17 mol % Example103 546000 2.9 174° C. 25mol % Example104 597000 2.7 182° C. 36 mol %

INDUSTRIAL APPLICABILITY

Use of the polymerization catalyst composition of the present inventionprovides novel production methods of various kinds of polymer compounds,and further provides novel polymer compounds.

The invention claimed is:
 1. A method of producing an olefin polymer,comprising: polymerizing an olefin monomer in the presence of apolymerization catalyst composition comprising: (1) a metallocenecomplex represented by the formula (I),

wherein: M is a central metal which is a group III metal atom or alanthanoid metal atom; Cp* is a ligand bound to the central metal andincludes a substituted or unsubstituted cyclopentadienyl derivative; Q¹and Q² are monoanionic ligands; and L is a neutral Lewis base, where wrepresents an integer of 0 to 3; and (2) an ionic compound composed of anon-ligand anion and a cation.
 2. The method according to claim 1,wherein the olefin monomer is one selected from the group consisting ofa substituted styrene, an unsubstituted styrene, ethylene, diene,norbornenes, and α-olefin.
 3. A method of producing an olefin copolymer,comprising: polymerizing two or more kinds of olefin monomers in thepresence of a polymerization catalyst composition comprising: (1) ametallocene complex represented by the formula (I),

wherein: M is a central metal which is a group III metal atom or alanthanoid metal atom; Cp* is a ligand bound to the central metal andincludes a substituted or unsubstituted cyclopentadienyl derivative; Q¹and Q² are monoanionic ligands; and L is a neutral Lewis base, where wrepresents an integer of 0 to 3; and (2) an ionic compound composed of anon-ligand anion and a cation.
 4. The method according to claim 3,wherein the olefin monomers are two or more kinds selected from thegroup consisting of a substituted styrene, an unsubstituted styrene,ethylene, diene, norbornenes, and α-olefin.
 5. The method according toclaim 1, wherein: the olefin polymer is a substituted or unsubstitutedstyrene polymer; and the olefin monomer is a substituted orunsubstituted styrene.
 6. The method according to claim 5, wherein thesubstituted or unsubstituted styrene polymer has a syndiotacticity of 80rrrr% or more in terms of a pentad indication.
 7. The method accordingto claim 6, wherein the polymer has Mw/Mn as an index of a molecularweight distribution of 1.7 or less.
 8. The method according to claim 3,wherein: the olefin copolymer is a styrene copolymer; and the olefinmonomers are two or more kinds of styrenes selected from a substitutedstyrene and an unsubstituted styrene.
 9. The method according to claim8, wherein the styrene copolymer has a syndiotacticity of 80 rrrr% ormore of a pentad indication.
 10. The method according to claim 9,wherein the copolymer has Mw/Mn as an index of a molecular weightdistribution of 1.7 or less.
 11. The method according to claim 3,wherein: the olefin copolymer is a copolymer of ethylene and asubstituted or unsubstituted styrene; and the olefin monomers areethylene and a substituted or unsubstituted styrene.
 12. The methodaccording to claim 11, wherein the copolymer of ethylene and asubstituted or unsubstituted styrene is a random copolymer and has asyndiotacticity of a chain composed of styrene structural units of 60 r% or more in terms of a diad indication; or is a block copolymer and hasa syndiotacticity of a styrene block chain of 80 rrrr % or more in termsof a pentad indication.
 13. The method according to claim 1, wherein:the olefin polymer is a 1,3-cyclohexadiene polymer; and the olefinmonomer is 1,3-cyclohexadiene.
 14. The method according to claim 13,wherein the 1,3-cyclohexadiene polymer has a ratio of a 1,4-structuralunit with respect to all structural units of 90% or more, and has acis-syndiotacticity of 70 rrrr % or more.
 15. The method according toclaim 3, wherein: the olefin copolymer is a copolymer of1,3-cyclohexadiene and a substituted or unsubstituted styrene; and theolefin monomers are 1,3-cyclohexadiene and a substituted orunsubstituted styrene.
 16. The method according to claim 15, wherein thecopolymer of 1,3-cyclohexadiene and a substituted or unsubstitutedstyrene has a ratio of a 1,4-structural unit with respect to allstructural units in the 1,3-cyclohexadiene of 90% or more.
 17. Themethod according to claim 3, wherein: the olefin copolymer is acopolymer of 1,3-cyclohexadiene and ethylene; and the olefin monomersare 1,3-cyclohexadiene and ethylene.
 18. The method according to claim17, wherein the copolymer of 1,3-cyclohexadiene and ethylene has a ratioof a 1,4-structural unit with respect to all structural units of the1,3-cyclohexadiene of 90% or more.
 19. The method according to claim 3,wherein: the olefin copolymer is a copolymer of ethylene, norbornenes,and a substituted or unsubstituted styrene; and the olefin monomers areethylene, norbornenes, and a substituted or unsubstituted styrene. 20.The method according to claim 19, wherein the copolymer is a randomcopolymer and has a syndiotacticity of a chain composed of styrenestructural units of 98 r % or more in terms of a diad indication. 21.The method according to claim 3, wherein: the olefin copolymer is acopolymer of dicyclopentadiene and ethylene; and the olefin monomers aredicyclopentadiene and ethylene.
 22. The method according to claim 21,wherein the copolymer of dicyclopentadiene and ethylene has a numberaverage molecular weight of 100,000 or more.
 23. The method according toclaim 3, wherein: the olefin copolymer is a copolymer of a substitutedor unsubstituted styrene and a conjugated diene; and the olefin monomersare a substituted or unsubstituted styrene and a conjugated diene. 24.The method according to claim 1, wherein, in the polymerization catalystcomposition, the central metal M contained in the metallocene complex isselected from the group consisting of Scandium (Sc), Gadolinium (Gd),Yttrium (Y), Holmium (Ho), Lutetium (Lu), Erbium (Er), Dysprosium (Dy),Terbium (Tb), and Thulium (Tm).
 25. The method according to claim 1,wherein, in the polymerization catalyst composition, the ligand Cp*including a cyclopentadienyl derivative is a non-crosslinking typeligand.
 26. The method according to claim 1, wherein, in thepolymerization catalyst composition, the cyclopentadienyl derivativecontained in the ligand Cp* in the metallocene complex istetramethyl(trimethylsilyl)cyclopentadienyl orpentamethylcyclopentadienyl.
 27. The method according to claim 1,wherein, in the polymerization catalyst composition, at least one of themonoanionic ligands Q¹ and Q² in the metallocene complex is atrimethylsilyl group.
 28. The method according to claim 1, wherein, inthe polymerization catalyst composition, the neutral Lewis base L in themetallocene complex is tetrahydrofran.
 29. The method according to claim3, wherein, in the polymerization catalyst composition, the centralmetal M contained in the metallocene complex is selected from the groupconsisting of Scandium (Sc), Gadolinium (Gd), Yttrium (Y), Holmium (Ho),Lutetium (Lu), Erbium (Er), Dysprosium (Dy), Terbium (Tb), and Thulium(Tm).
 30. The method according to claim 3, wherein, in thepolymerization catalyst composition, the ligand Cp* including acyclopentadienyl derivative is a non-crosslinking type ligand.
 31. Themethod according to claim 3, wherein, in the polymerization catalystcomposition, the cyclopentadienyl derivative contained in the ligand Cp*in the metallocene complex istetramethyl(trimethylsilyl)cyclopentadienyl orpentamethylcyclopentadienyl.
 32. The method according to claim 3,wherein, in the polymerization catalyst composition, at least one of themonoanionic ligands Q¹ and Q² in the metallocene complex is atrimethylsilyl group.
 33. The method according to claim 3, wherein, inthe polymerization catalyst composition, the neutral Lewis base L in themetallocene complex is tetrahydrofran.
 34. The method according to claim12, wherein the copolymer has Mw/Mn as an index of a molecular weightdistribution of 1.3 or less.
 35. The method according to claim 12,wherein a ratio of the styrene structural unit with respect to allstructural units is 5 to 99 mol %.
 36. The method according to claim 16,wherein the copolymer is a random copolymer and has a syndiotacticity ofa chain composed of styrene structural units of 98 r % or more in termsof a diad indication.
 37. The method according to claim 22, wherein thecopolymer has a ratio of a dicyclopentadiene structural unit withrespect to all structural units of 10 mol % or more.